CN1488010A - Surface-treated metal sheets excellent in press dragging resistance and coil deformation resistance and process for producing the same - Google Patents
Surface-treated metal sheets excellent in press dragging resistance and coil deformation resistance and process for producing the same Download PDFInfo
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- CN1488010A CN1488010A CNA028038606A CN02803860A CN1488010A CN 1488010 A CN1488010 A CN 1488010A CN A028038606 A CNA028038606 A CN A028038606A CN 02803860 A CN02803860 A CN 02803860A CN 1488010 A CN1488010 A CN 1488010A
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- polyolefin
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- water
- inorganic composite
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 139
- 239000002184 metal Substances 0.000 title claims abstract description 138
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- 239000007787 solid Substances 0.000 claims abstract description 52
- 229920000098 polyolefin Polymers 0.000 claims abstract description 50
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 230
- 239000002131 composite material Substances 0.000 claims description 156
- 239000000314 lubricant Substances 0.000 claims description 143
- 238000000576 coating method Methods 0.000 claims description 140
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- 239000000463 material Substances 0.000 description 21
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- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 4
- 229910052912 lithium silicate Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 4
- 229910052913 potassium silicate Inorganic materials 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
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- 239000004793 Polystyrene Substances 0.000 description 3
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- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
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- 229910052742 iron Inorganic materials 0.000 description 3
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
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- 229910052749 magnesium Inorganic materials 0.000 description 2
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- 238000007669 thermal treatment Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
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- RHAXKFFKGZJUOE-UHFFFAOYSA-N 7-acetyl-6-ethyl-3,5,8-trihydroxy-9,10-dioxoanthracene-1,2-dicarboxylic acid Chemical compound O=C1C2=CC(O)=C(C(O)=O)C(C(O)=O)=C2C(=O)C2=C1C(O)=C(CC)C(C(C)=O)=C2O RHAXKFFKGZJUOE-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 241000896365 Haplothrips statices Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
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- 150000003818 basic metals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 229910052793 cadmium Inorganic materials 0.000 description 1
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- 230000021523 carboxylation Effects 0.000 description 1
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- 238000004532 chromating Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- YARNEMCKJLFQHG-UHFFFAOYSA-N prop-1-ene;styrene Chemical compound CC=C.C=CC1=CC=CC=C1 YARNEMCKJLFQHG-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Laminated Bodies (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Surface-treated metal sheets comprising 0.3-5.0 g/m<2> of a film formed from an aqueous organic/inorganic compound paint containing (1) a polyolefin wax dispersion with a molecular weight of 6000-15,000 or (2) a polyolefin wax dispersion with a molecular weight of 6000-15,000 (A) and a polyolefin wax dispersion (B) with a molecular weight of 1000-5000, with 5-35 wt% of colloidal silica in terms of solid content. Also, surface-treated metal sheets having, as a first layer, an aqueous organic/inorganic compound film containing a polyolefin wax dispersion with a molecular weight of 6000-15,000, at a dry weight of 0.05-0.3 g/m<2>, and as a second layer, an aqueous organic/inorganic compound film containing 5-35 wt% of colloidal silica in terms of solid content, at a dry weight of 0.5-5.0 g/m<2>. There are also provided an aqueous organic/inorganic compound paint and a manufacturing process, which allow manufacture of such surface-treated metal sheets.
Description
Technical field
The water-based organic/inorganic composite coating that the present invention relates to be applicable to the surface-treated metal plate and the manufacture method thereof of automobile, household electrical appliance and material of construction etc. and can be used for obtaining described surface-treated metal plate, described surface-treated metal plate not only shows excellent performance such as solidity to corrosion, sticking power and weldability, and shows excellent resistance to compression system scratch property and anti-Texturized property.
The invention still further relates to surface-treated metal plate and manufacture method thereof that is applicable to automobile, household electrical appliance and material of construction etc. and the water-based organic/inorganic composite coating that can be used for obtaining described surface-treated metal plate, described surface-treated metal plate not only shows excellent performance such as solidity to corrosion, sticking power and weldability, and shows excellent resistance to compression system scratch property and anti-continuous skimming wear.
The invention still further relates to the surface-treated metal plate that is applicable to automobile, household electrical appliance and material of construction etc., show excellent performance such as solidity to corrosion, sticking power and weldability and keep resistance to compression system scratch property, improve simultaneously in the section bundling process because of reeling loose or the folding problem that causes the coiled material fragmentation of load, and be suppressed in the pressing process generation that breaks away from the adhering residue thing that film causes by lubricant.
Background technology
Surface treated steel plate of having developed so far such as electrogalvanizing steel plate and hot-dip galvanized steel sheet are widely used for household electrical appliance, material of construction and automobile component etc.These steel plates pass through chromate treating or phosphatizing mostly to improve solidity to corrosion and coating adhesion.
In addition, along with being that the no coatings applications of purpose increases recently to reduce step and to reduce cost, particularly in electrical equipment industry, performance requriements to the surface of steel plate visual appearance improves constantly, not only comprise solidity to corrosion and coating adhesion, and comprise resistance to marring, anti-impression of the hand and condensation or the wetting susceptibility that causes variable color.
Require required performance for satisfying the human consumer, developed the coating metal plate that special resin base organic hybrid films is arranged on the deposited steel plating plate of chromate treating.For example, Japan has examined and discloses a kind of production method with the surface treated steel plate that improves performance such as solidity to corrosion and anti-impression of the hand among patent publications (disclosing) No.4-14191 (JP-A-4-14191), is wherein forming on the steel plate of chromium plating chromate coatings by add the organic hybrid films of certain detail seed lac body colloidal sol preparation in water-soluble organic resin.
Japanese unexamined patent publication No. publication (disclosing) No.3-39485 (JP-A-3-39485) discloses after carrying out chromate treating on the steel plate of zinc-plated Base Metal, 0.3-3.0g/m
2Silicon-dioxide that is dispersed in the water soluble resin the comprising of dry weight fraction of coverage and second-order transition temperature (Tg) are the coating of 40 ℃ or higher wax.And Japanese unexamined patent publication No. publication (disclosing) No.3-28380 (JP-A-3-28380) discloses behind chromate treating on the steel plate of electro-galvanizing by 0.5-4.0g/m
2The dry weight fraction of coverage comprise carboxylation polyvinyl resin and Teflon
TMThe lubricated coating steel plate that the coating of lubricant obtains.But, also develop surface treated steel plate with improvement oilness by in organic membrane, adding solid lubricant for satisfying for example requirement of press formability of the strong resistance to marring of consumer wants.For example, Japanese unexamined patent publication No. publication (disclosing) No.6-173037 (JP-A-6-173037) discloses the steel plate by the band lubricant film that adds silicon-dioxide and polyolefin-wax acquisition in ether/ester type polyurethane resin and Resins, epoxy.
Disclosed technology provides and has had the sheet material that the excellent properties balance comprises solidity to corrosion, coating adhesion, anti-impression of the hand and variable color susceptibility among Japanese unexamined patent publication No. publication (disclosing) No.4-14191 (JP-A-4-14191), at present as one of main raw of household electrical appliance.Even but the surface treated steel plate of this coating organic membrane also shows cut, the scratch in the pressing operation process and the wearing and tearing in the Product transport process etc. in the cargo handling process sometimes.
By contrast, disclosed technique table reveals scratch or the wearing and tearing in the pressing operation process of low degree among Japanese unexamined patent publication No. publication (disclosing) No.3-39485 (JP-A-3-39485) and Japanese unexamined patent publication No. publication (disclosing) No.3-28380 (JP-A-3-28380), and disclosed technology even in violent operation as also still have excellent resistance to compression system under the press forming and abrade property among Japanese unexamined patent publication No. publication (disclosing) No.6-173037 (JP-A-6-173037).But, the surface of steel plate of producing by disclosed technology among Japanese unexamined patent publication No. publication (disclosing) No.3-39485 (JP-A-3-39485), Japanese unexamined patent publication No. publication (disclosing) No.3-28380 (JP-A-3-28380) and Japanese unexamined patent publication No. publication (disclosing) No.6-173037 (JP-A-6-173037) easily slides, thereby is accompanied by in the section bundling process because of reeling loose or the folding problem that causes the coiled material fragmentation of load.Improve pulling force in the coiled material rolling-in process for the measure of avoiding these problems to take is included at present, it is loose that increase bandage quantity prevents to pack the back coiled material.
First main purpose of the present invention is to have that controlled film is formed and the surface-treated metal plate and the manufacture method thereof of the kinetic friction coefficient on controlled film surface and static friction coefficient and can be used for making the water-based organic/inorganic composite coating of described surface-treated metal plate by providing, guarantee excellent solidity to corrosion, sticking power and weldability performance and keep resistance to compression system scratch property, improve simultaneously in the section bundling process because of reeling loose or the folding problem that causes the coiled material fragmentation of load.
Second main purpose of the present invention provides to be had excellent solidity to corrosion, sticking power and weldability performance and has the water-based organic/inorganic composite coating that excellent resistance to compression system abrades the surface-treated metal plate and the manufacture method thereof of property and anti-continuous skimming wear and can be used for making described surface-treated metal plate.
The 3rd main purpose of the present invention provides a kind of surface-treated metal plate and manufacture method thereof, described surface-treated metal plate shows excellent performance such as solidity to corrosion, sticking power and weldability and maintenance resistance to compression system scratch property, improve simultaneously in the section bundling process because of reeling loose or the folding problem that causes the coiled material fragmentation of load, and be suppressed in the pressing process generation that breaks away from the adhering residue thing that film causes by lubricant.
Summary of the invention
For realizing above-mentioned first purpose, the inventor is through a lot of industrious researchs, finish the present invention based on following discovery: comprising molecular weight by coating on the overlay metallization plate is that the polyolefin-wax dispersion of 6000-15000 is with the water-based organic/inorganic composite coating and the drying of colloidal silica form the water-based organic/inorganic composite film in right amount, can obtain not only to show excellent performance such as solidity to corrosion, sticking power and weldability, and showing the excellent resistance to compression system scratch property and the surface-treated metal plate of anti-Texturized property, wherein said metal sheet surface has the kinetic friction coefficient that is controlled at 0.07-0.15 and is controlled at 0.10 or higher static friction coefficient.
Therefore, according to its first aspect, main points of the present invention are as follows.
(1) surface-treated metal plate of a kind of resistance to compression system scratch property and anti-Texturized property excellence is characterised in that to have 0.3-5.0g/m
2Comprise polyolefin-wax dispersion that one of water soluble resin and silicate compound or both and molecular weight are 6000-15000 and by the water-based organic/inorganic composite membrane of the colloidal silica of solid content 5-35% weight.
(2) according to the surface-treated metal plate of the resistance to compression system of above (1) scratch property and anti-Texturized property excellence, be characterised in that described polyolefin-wax dispersion be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a in the modified polyolefin wax dispenser of 0.1-5.0 μ m.
(3) according to the resistance to compression system scratch property of above (1) or (2) and the surface-treated metal plate of anti-Texturized property excellence, the kinetic friction coefficient that is characterised in that described surface is 0.07-0.15, and static friction coefficient is 0.10 or higher.
(4) a kind of water-based organic/inorganic composite coating is characterised in that to comprise polyolefin-wax dispersion, the colloidal silica by solid content 5-35% weight, the He Shui that one of water soluble resin and silicate compound or both and molecular weight are 6000-15000.
(5) the water-based organic/inorganic composite coating of above (4), be characterised in that described polyolefin-wax dispersion be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a in the modified polyolefin wax dispenser of 0.1-5.0 μ m.
(6) manufacture method of the surface-treated metal plate of a kind of resistance to compression system scratch property and anti-Texturized property excellence is characterised in that the coating of above (4) is pressed dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
(7) manufacture method of the surface-treated metal plate of a kind of resistance to compression system scratch property and anti-Texturized property excellence is characterised in that the coating of above (5) is pressed dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
For realizing above-mentioned second purpose, the inventor is through a lot of industrious researchs, finish the present invention based on following discovery: comprise polyolefin-wax dispersion that molecular weight is 6000-15000, polyolefin-wax dispersion that molecular weight is 1000-5000 and the water-based organic/inorganic composite coating and the dry water-based organic/inorganic composite film that forms of an amount of colloidal silica by coating on the overlay metallization plate, can obtain the surface-treated metal plate of resistance to compression system scratch property and anti-continuous skimming wear excellence.
Therefore, according to its second aspect, main points of the present invention are as follows.
(1) surface-treated metal plate of a kind of resistance to compression system scratch property and anti-continuous skimming wear excellence, be characterised in that to have and comprise one of water soluble resin and silicate compound or both and be the lubricant (A) formed of the polyolefin-wax dispersion of 6000-15000, be the lubricant (B) formed of the polyolefin-wax dispersion of 1000-5000 and by the water-based organic/inorganic composite membrane of the colloidal silica of solid content 5-35% weight with have 0.3-5.0g/m by molecular weight by molecular weight
2Described water-based organic/inorganic composite membrane.
(2) according to the resistance to compression system scratch property of above (1) and the surface-treated metal plate of anti-continuous skimming wear excellence, be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant of the modified polyolefin wax dispenser of 0.1-5.0 μ m, lubricant (B) is that polar functionalities, molecular weight are not that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-5.0 μ m.
(3) a kind of water-based organic/inorganic composite coating comprises one of water soluble resin and silicate compound or both and is the lubricant (A) formed of the polyolefin-wax dispersion of 6000-15000, is lubricant (B), the colloidal silica by solid content 5-35% weight, the He Shui that the polyolefin-wax dispersion of 1000-5000 is formed by molecular weight by molecular weight.
(4) according to the water-based organic/inorganic composite coating of above (3), be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the modified polyolefin wax dispenser of 0.1-5.0 μ m, lubricant (B) is that polar functionalities, molecular weight are not that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-5.0 μ m.
(5) manufacture method of the surface-treated metal plate of a kind of resistance to compression system scratch property and the moving abradability excellence of antiskid is characterised in that the coating of above (3) is pressed dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
(6) manufacture method of the surface-treated metal plate of a kind of resistance to compression system scratch property and anti-continuous skimming wear excellence is characterised in that the coating of above (4) is pressed dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
For realizing above-mentioned the 3rd purpose, the inventor is through a lot of industrious researchs, finish the present invention based on following discovery: comprising by molecular weight by coating on the upper strata of overlay metallization plate is the lubricant (A) that the polyolefin-wax dispersion of 6000-15000 is formed, be the water-based organic/inorganic composite coating (E) of the lubricant (B) formed of the polyolefin-wax dispersion of 1000-5000 when needing by molecular weight, baking forms the first layer, coating comprises the water-based organic/inorganic composite coating (F) of an amount of colloidal silica then, and baking forms the second layer, can obtain a kind of surface-treated metal plate, wherein the kinetic friction coefficient of described metal sheet surface can be controlled at 0.07-0.15 and static friction coefficient is controlled at 0.10 or higher, also prevent from pressing process to break away from the generation of the adhering residue thing that film causes simultaneously by lubricant.
Therefore, according to its third aspect, main points of the present invention are as follows.
(1) surface-treated metal plate of a kind of resistance to compression system scratch property and anti-Texturized property excellence is characterised in that to have 0.05-0.3g/m
2Dry weight comprise one of water soluble resin and silicate compound or both and by molecular weight be the water-based organic/inorganic composite membrane (C) of the lubricant (A) formed of the polyolefin-wax dispersion of 6000-15000 as the first layer, and 0.5-5.0g/m
2The water-based organic/inorganic composite membrane of forming by one of water soluble resin and silicate compound or both with by the colloidal silica of solid content 5-35% weight (D) of dry weight is as the second layer.
(2) according to the surface-treated metal plate of the resistance to compression system of above (1) scratch property and anti-Texturized property excellence, be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the modified polyolefin wax dispenser of 0.1-5.0 μ m.
(3), be characterised in that described water-based organic/inorganic composite membrane (C) is that the compounded lubricant that the lubricant (B) of the lubricant (A) of polyolefin-wax dispersion of 6000-15000 and the polyolefin-wax dispersion that molecular weight is 1000-5000 is mixed with is formed by water soluble resin with by molecular weight according to the surface-treated metal plate of the resistance to compression system of above (1) or (2) scratch property and anti-Texturized property excellence.
(4) according to the resistance to compression system scratch property of above (3) and the surface-treated metal plate of anti-Texturized property excellence, be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the modified polyolefin wax dispenser of 0.1-5.0 μ m, lubricant (B) is that polar functionalities, molecular weight are not that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-3.0 μ m.
(5) according to above (1) to (4) each resistance to compression system scratch property and the surface-treated metal plate of anti-Texturized property excellence, the kinetic friction coefficient that is characterised in that described surface is 0.07-0.15, static friction coefficient is 0.10 or higher.
(6) manufacture method of the surface-treated metal plate of a kind of resistance to compression system scratch property and anti-Texturized property excellence is characterised in that on overlay metallization plate coating is that the lubricant (A) of polyolefin-wax dispersion of 6000-15000 and the water-based organic/inorganic composite coating (E) that water is formed extremely reach 0.05-0.3g/m by dry weight basis by one of water soluble resin and silicate compound or both and molecular weight
2Afterwards, baking forms the first layer, be coated with then by one of water soluble resin and silicate compound or both and wherein colloidal silica content count the colloidal silica of 5-35% weight by solid content and water-based organic/inorganic composite coating (F) that water is formed extremely reaches 0.5-5.0g/m by dry weight basis
2, baking forms the second layer.
(7) according to the manufacture method of the surface-treated metal plate of the resistance to compression system of above (6) scratch property and anti-Texturized property excellence, be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the modified polyolefin wax dispenser of 0.1-5.0 μ m.
(8), be characterised in that described water-based organic/inorganic composite coating (E) is that compounded lubricant and the water that the lubricant (B) of the lubricant (A) of polyolefin-wax dispersion of 6000-15000 and the polyolefin-wax dispersion that molecular weight is 1000-5000 is mixed with is formed by water soluble resin, by molecular weight according to the manufacture method of the surface-treated metal plate of the resistance to compression system of above (6) or (7) scratch property and anti-Texturized property excellence.
(9) according to above (6) to (8) each resistance to compression system scratch property and the manufacture method of the surface-treated metal plate of anti-Texturized property excellence, be characterised in that described lubricant (A) is to be selected from not polar functionalities, molecular weight is that 6000-15000 and granularity are the polyolefin-wax dispersion of 0.1-5.0 μ m, with molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the modified polyolefin wax dispenser of 0.1-5.0 μ m, lubricant (B) is a polar functionalities not, molecular weight is that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-3.0 μ m.
The accompanying drawing summary
Fig. 1 is the diagram according to the surface-treated metal plate of first aspect present invention.
Fig. 2 is the diagram according to the surface-treated metal plate of second aspect present invention.
Fig. 3 is the diagram according to a kind of embodiment of the surface-treated metal plate of third aspect present invention.
Fig. 4 is the diagram according to the another embodiment of the surface-treated metal plate of third aspect present invention.
Preferred forms
Explain the present invention in more detail below.
The ordinary method that is used for improving the resistance to compression system scratch property of water-based organic/inorganic compound coating steel plate is that the water-based organic/inorganic composite membrane on steel plate adds lubricant such as low-molecular-weight polyolefin wax.By in water-based organic/inorganic film, adding the not low-molecular-weight polyolefin wax of polar functionalities in this way, described wax is present in the film surface with particle form, thereby can reduce the avidity of metal sheet surface, described wax is also crushed in pressing operation simultaneously forms lubricant film between steel plate and punch die.Thereby obtain excellent lubricating effect, thereby can reduce the scratch in the pressing process.
According to first aspect present invention, molecular weight is that the polyolefin-wax dispersion of 6000-15000 is used as lubricant with specified amount in water-based organic/inorganic composite coating.Described composite coating transfers to the content of colloidal silica and counts 5-35% weight by solid content.
Fig. 1 illustrates a kind of embodiment of surface-treated metal plate of the present invention.Surface-treated metal plate of the present invention has such structure: water-based organic/inorganic composite membrane 2 is arranged on overlay metallization plate 3.Described water-based organic/inorganic composite membrane 2 is to be coated with on overlay metallization plate 3 by proper method to comprise one of water soluble resin and silicate compound or both and colloidal silica, water and form as the water-based organic/inorganic composite coating of the polyolefin-wax dispersion 1 of lubricant.As shown in fig. 1, described polyolefin-wax dispersion 1 is exposed from water-based organic/inorganic composite membrane 2 with particle form.
Therefore, in water-based organic/inorganic composite membrane, add the polyolefin-wax dispersion, and the molecular weight of described wax is transferred to appropriate value, thereby on the film surface, produce the wax of particle form and control the hardness of described wax and the avidity on film surface.Also regulate dioxide-containing silica, not only for the hardness of film but also for obtaining film properties such as solidity to corrosion and sticking power.Thereby the surface-treated metal plate that can obtain not only to have satisfied solidity to corrosion and sticking power but also have still undiscovered excellent anti compacting scratch property and anti-Texturized property in the prior art, it has the kinetic friction coefficient that is controlled at 0.07-0.15 and is controlled at 0.10 or higher static friction coefficient.
Explained later abrades the manufacture method of the surface-treated metal plate of property and anti-Texturized property excellence according to the resistance to compression system of first aspect present invention.
Be applied on the basic overlay metallization plate and baking forms water-based organic/inorganic composite membrane and makes according to the surface-treated metal plate of the first aspect present invention water-based organic/inorganic composite coating by will regulation.Be applicable to that basic overlay metallization plate of the present invention comprises plating, the steel plate of hot dip process and evaporation zinc-base metal, aluminize or the metal sheet of aluminium alloy, the metal sheet of the metal sheet of lead plating or lead alloy and zinc-plated or tin alloy, as galvanized metal sheet, the metal sheet of zinc-plated-nickel, the metal sheet of zinc-plated-iron, the metal sheet of zinc-plated-chromium, the metal sheet of zinc-plated-aluminium, the metal sheet of zinc-plated-titanium, the metal sheet of zinc-plated-magnesium, the metal sheet of zinc-plated-manganese etc., and the little cobalt of containing is arranged, molybdenum, tungsten, nickel, titanium, chromium, aluminium, manganese, iron, magnesium, plumbous, antimony, tin, copper, cadmium, arsenic etc. are as this coating of independent metallic element or impurity and/or wherein be dispersed with inorganics such as silicon-dioxide, those of aluminum oxide or titanium oxide.The present invention also can be used for compound overlay metallization plate, wherein above-mentioned coating and other coating such as iron plating or iron-combinations such as phosphorus coating.
The coating fraction of coverage of every kind of overlay metallization plate is preferably every side 1g/m at least
2, because lower fraction of coverage causes solidity to corrosion to reduce.
Surface-treated metal plate of the present invention can be by improving sticking power or the acquisition of corrosion proof base conditioning to described overlay metallization plate before forming described water-based organic/inorganic composite membrane.Also can be by directly on without the overlay metallization plate of base conditioning, forming described water-based organic/inorganic composite membrane acquisition.Described base conditioning does not have particular restriction, as long as it can achieve the above object, but general preferred chromate treating, because it can improve solidity to corrosion or sticking power.
As the method that forms chromate film, for example can mention contain chromic anhydride, chromic salt or dichromate as the aqueous solution of main agents in dipping (reactivity) chromate treating or electrolytic chromate handle, or the coating chromating, wherein will comprise the treatment solution coating of mixture of colloidal silica etc. and dry under the situation of not washing then in the described aqueous solution.
The chromic salt fraction of coverage is preferably about 5-100mg/m
2(based on Cr).If fraction of coverage is lower than 5mg/m
2(based on Cr), gained solidity to corrosion deficiency then is and if be higher than 100mg/m
2, the interior poly-deficiency of chromate film itself then takes place, thereby reduces coating adhesion.
Can use acrylate-acrylic copolymer, epoxy-acrylic copolymer, olefin-acrylic multipolymer, alkene ion-exchange polymer, styrene-propene acid copolymer, ammonia ester-acrylic copolymer, ammonia ester-Resins, epoxy, ethene-imines-acrylic resin etc. as water soluble resin.In order to obtain coating, preferably make described resin dispersion become to form emulsion in the solvent at water with these water soluble resins.When needing, also can add various linking agents such as melamine resin or aminoresin.Wherein, from performance and cost, especially preferably use acrylic based resin such as olefin-acrylic multipolymer.Under the situation of the violent press forming of needs, the preferred use demonstrates hardness and ductile ammonia ester-epoxy.
Being used for silicate compound of the present invention generally represents with following formula: M
2OnSiO
2(wherein M is one of basic metal that is selected from sodium, potassium and lithium, and n is the value of any needs), it is one or more the mixture that is selected from water glass, potassium silicate and the lithium silicate.As M
2O and SiO
2" n " value of mol ratio preferred in the scope of 1-10.Preferably " n " value is not less than 1, otherwise the gained film is tending towards moisture absorption and film sticking power deficiency.Preferably be no more than 10, otherwise the gained film becomes fragile and formability descends.
Be applicable to that colloidal silica of the present invention can be spherical or thread silicon-dioxide, or the dendritic string of bonding pearl colloidal silica.Under the situation of preparing spherical SiO 2, granularity is preferably 5-50nm, under the situation of thread silicon-dioxide, diameter is preferably 5-50nm, it is 1-5 that described wire chemical is bonded to length/thickness rate, and under the situation of the dendritic string of pearl silicon-dioxide, the ratio of [mean particle size of the length of aggregate/pearl silicon-dioxide] is preferably at least 4, and one or more branch is arranged.
Described colloidal silica adds in the water-based organic/inorganic composite coating of the present invention with 5-35% weight by solid content.When being lower than 5% weight, can not obtain enough solidity to corrosions and resistance to compression system scratch property, and during greater than 35% weight, coating adhesion and resistance to compression system scratch property are relatively poor.
The used water-based organic/inorganic composite coating of first aspect present invention is to be the polyolefin-wax dispersion combined preparation of 6000-15000 by one of above-mentioned water soluble resin and silicate compound or both and colloidal silica and water and molecular weight.More preferably in described water-based organic/inorganic composite coating, add be selected from be substantially free of polar group, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a in the modified polyolefin wax dispenser of 0.1-5.0 μ m.
As the polyolefin-wax dispersion, can use the polyethylene wax, Poly Propylene Wax or the polybutene wax that are substantially free of polar group at water or contain concentration and be not more than 5% emulsifying agent, preferably do not contain dispersion in the aqueous solution of emulsifying agent.
As the modified polyolefin wax dispenser, can use the polyethylene wax, Poly Propylene Wax or the polybutene wax that contain polar group at water or contain concentration and be not more than 5% emulsifying agent, preferably do not contain dispersion in the aqueous solution of emulsifying agent.Described polar group can be introduced (the polyene wax of oxidation) by with oxygenant such as oxygen, ozone, nitric acid etc. polyolefin-wax is carried out oxide treatment in the presence of catalyzer, also can by make ethylenic unsaturated carboxylic acid monomer such as vinylformic acid, methacrylic acid, Ba Dousuan, toxilic acid, fumaric acid, methylene-succinic acid etc. and polyolefin-wax be dissolved in crude benzol etc., then nitrogen gas stream and polymerization starter (superoxide, redox agent, heavy metal catalyst etc.) down the heating grafting introduce.
The average particle size of described polyolefin-wax dispersion and modified polyolefin wax dispenser is preferably 0.1-5.0 μ m, more preferably 1.0-4.0 μ m.Described average particle size preferably is not less than 0.1 μ m, otherwise is tending towards causing assembling and infringement stability.Described average particle size also preferably is not more than 5.0 μ m, otherwise the stability decreases of dispersion.The ratio of described average particle size and number average particle size preferably make average particle size/number average particle size less than 3 scope in.
The weight average molecular weight range of described polyolefin-wax dispersion and modified polyolefin wax dispenser is preferably 6000-15000.Preferred described weight-average molecular weight is not less than 6000, otherwise causes anti-Texturized property poor.Preferred described weight-average molecular weight is not more than 15000, otherwise infringement resistance to compression system scratch property.
The analytical procedure and the condition of the weight-average molecular weight of described polyolefin-wax dispersion and modified polyolefin wax dispenser are described below, but described molecular weight analyse is not necessarily limited to this method.
Analytical procedure: high temperature GPC (gel permeation chromatography)
Post: PS (polystyrene) gel mixed type (2-4 post series connection)
Solvent: orthodichlorobenzene (ODCB), trichlorobenzene (TCB) etc.
Measure temperature: 130-140 ℃
Detector: differential refractometer (RI) or infrared detector
Working curve: be purchased the molecular weight that monodispersity PS converts based on using
As JIS K 5902 defineds, the acid number of described modified polyolefin wax dispenser (KOH-mg/g) scope is preferably 40 or lower.If acid number surpasses 40, then described lubricant hardening and can not obtain enough oilnesies.
Described polyolefin-wax dispersion and modified polyolefin wax dispenser also preferably have 950-1000kg/m
3Density (as JIS K 6760 defineds), 0.2mm or lower hardness (acupuncture hardness) (as JIS K 2207 defineds), 80% or bigger degree of crystallinity (measuring) and 110-150 ℃ fusing point by X-ray diffraction.
Being selected from least a in these polyolefin-wax dispersions and the modified polyolefin wax dispenser preferably is included in the described water-based organic/inorganic composite coating in 1-30 weight % (by solid content).During less than 1 weight %, can not obtain enough resistance to compression system scratch property, and during greater than 30 weight %, coating adhesion is poor.
The fraction of coverage scope of described water-based organic/inorganic composite membrane is 0.3-5.0g/m
2(pressing dry weight basis).More preferably 1.0-3.0g/m
2Preferred fraction of coverage is not less than 0.3g/m
2To realize target resistance to compression system scratch property, preferably be not more than 5.0g/m
2Be beneficial to weldability.
It can be spraying, curtain coating, flow coat, roller coat, blade coating, brushing, dip-coating, air knife blade coating etc. that coating forms described water-based organic/inorganic composite membrane method therefor.
Storing temperature is preferably 80-250 ℃.Even more preferably temperature be higher than fusing point with lubricator.When being lower than 80 ℃, solidity to corrosion is descended, and when surpassing 250 ℃, film overvulcanization and formability is reduced because of the water in the coating can not evaporate fully.
Drying plant is not had particular restriction, and method therefor can be the combination that warm air sprays, uses well heater indirect heating, infrared heating, inductance heating or these methods.
The kinetic friction coefficient on surface-treated metal plate of the present invention surface is preferably 0.07-0.15, and static friction coefficient is preferably 0.10 or higher.Kinetic friction coefficient is higher than at 0.15 o'clock, and resistance to compression system scratch property is poor, and kinetic friction coefficient be lower than 0.07 or static friction coefficient be lower than at 0.10 o'clock, anti-Texturized property is poor.
According to second aspect present invention, in water-based organic/inorganic composite coating, add the lubricant with different molecular weight (A) of specified amount and (B) as lubricant.Here, molecular weight be the polyolefin-wax dispersion of 6000-15000 as lubricant (A), molecular weight is that the polyolefin-wax dispersion of 1000-5000 is as lubricant (B).Also transfer to by solid content and count 5-35% weight, can reach film hardness and film properties for example solidity to corrosion and sticking power by dioxide-containing silica with described water-based organic/inorganic composite membrane.
Fig. 2 illustrates a kind of embodiment of surface-treated metal plate of the present invention.Surface-treated metal plate of the present invention has such structure: water-based organic/inorganic composite membrane 13 is arranged on overlay metallization plate 14.Described water-based organic/inorganic composite membrane 13 is to be coated with on overlay metallization plate 14 by proper method to comprise one of water soluble resin and silicate compound or both and lubricant (A), lubricant (B), form by the colloidal silica of solid content 5-35% weight and the water-based organic/inorganic composite coating of water.As shown in Figure 2, lubricant (A) 11 and lubricant (B) 12 expose from water-based organic/inorganic composite membrane 13 with particle form.
Therefore, low-molecular-weight polyolefin wax dispenser and high molecular polyolefine wax dispenser commonly used are all added in the water-based organic/inorganic composite membrane, suppress the fragmentation of wax in pressing mold and the continuous sliding process with the wax that on the film surface, produces particle form simultaneously.Also regulate dioxide-containing silica, not only for the hardness of film but also for reaching film properties such as solidity to corrosion and sticking power.Thereby not only can obtain satisfied solidity to corrosion and sticking power, but also improve the time length of lubricating effect in resistance to compression system scratch property and the continuous sliding process.
Explained later is according to the resistance to compression system scratch property of second aspect present invention and the manufacture method of the surface-treated metal plate of anti-continuous skimming wear excellence.This manufacture method is basic identical with the manufacture method according to the surface-treated metal plate of first aspect present invention, but institute's use organic/inorganic composite coating difference.
Also the water-based organic/inorganic composite coating by will regulation is applied on the basic overlay metallization plate and baking forms water-based organic/inorganic composite membrane and makes according to the surface-treated metal plate of second aspect present invention.
Be applicable to basic overlay metallization plate of the present invention as the front at as described in the surface-treated metal plate of first aspect present invention.The coating fraction of coverage of every kind of overlay metallization plate is preferably every side 1g/m at least
2, because lower fraction of coverage causes solidity to corrosion to reduce.Form described water-based organic/inorganic composite membrane after can be before forming described water-based organic/inorganic composite membrane described overlay metallization plate being improved sticking power or corrosion proof base conditioning, also can be directly on without the overlay metallization plate of base conditioning the described water-based organic/inorganic composite membrane of formation.Described base conditioning there is not particular restriction, as long as can achieve the above object, but general preferred chromate treating, because it can improve solidity to corrosion or sticking power.Described chromic salt film and chromic salt fraction of coverage as the front at as described in the surface-treated metal plate of first aspect.
As water soluble resin, can use the front at mentioned those of the surface-treated metal plate of first aspect.For obtaining coating, equally preferably make described resin dispersion become to form emulsion in the solvent at water, when needing, also can add various linking agents such as melamine resin or aminoresin.From performance and cost, especially preferably use acrylic based resin such as olefin-acrylic multipolymer.Under the situation of the violent press forming of needs, or under the situation of the bigger anti-continuous skimming wear of needs, the preferred use demonstrates hardness and ductile ammonia ester-epoxy.
The silicate compound that is used for second aspect present invention and colloidal silica can described those be identical at the surface-treated metal plate of first aspect with the front.
Described colloidal silica adds in the described water-based organic/inorganic composite coating with 5-35% weight by solid content.When being lower than 5% weight, can not obtain enough solidity to corrosions and resistance to compression system scratch property, and during greater than 35% weight, coating adhesion and resistance to compression system scratch property are relatively poor.
The used water-based organic/inorganic composite coating of second aspect present invention is by the lubricant with different molecular weight (A) of one of above-mentioned water soluble resin and silicate compound or both and colloidal silica and water and specified amount and (B) combined preparation.Here, molecular weight be the polyolefin-wax dispersion of 6000-15000 as lubricant (A), molecular weight is that the polyolefin-wax dispersion of 1000-5000 is as lubricant (B).More preferably, with be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the modified polyolefin wax dispenser of 0.1-5.0 μ m as lubricant (A), be that 1000-5000 and granularity are that the polyolefin-wax dispersion of 0.1-5.0 μ m is as lubricant (B) with not polar functionalities, molecular weight.
As the polyolefin-wax dispersion, can use the polyethylene wax, Poly Propylene Wax or the polybutene wax that are substantially free of polar group at water or contain concentration and be not more than 5% emulsifying agent, preferably do not contain dispersion in the aqueous solution of emulsifying agent.
As the modified polyolefin wax dispenser, can use the polyethylene wax, Poly Propylene Wax or the polybutene wax that contain polar group at water or contain concentration and be not more than 5% emulsifying agent, preferably do not contain dispersion in the aqueous solution of emulsifying agent.Described polar group can be introduced (the polyene wax of oxidation) by with oxygenant such as oxygen, ozone, nitric acid etc. polyolefin-wax is carried out oxide treatment in the presence of catalyzer, also can by make ethylenic unsaturated carboxylic acid monomer such as vinylformic acid, methacrylic acid, Ba Dousuan, toxilic acid, fumaric acid, methylene-succinic acid etc. and polyolefin-wax be dissolved in crude benzol etc., then nitrogen gas stream and polymerization starter (superoxide, redox agent, heavy metal catalyst etc.) down the heating grafting introduce.
The average particle size of described polyolefin-wax dispersion and modified polyolefin wax dispenser is preferably 0.1-5.0 μ m, more preferably 1.0-4.0 μ m.Described average particle size preferably is not less than 0.1 μ m, otherwise is tending towards causing assembling and infringement stability.Described average particle size also preferably is not more than 5.0 μ m, otherwise the stability decreases of dispersion.The ratio of described average particle size and number average particle size preferably make average particle size/number average particle size less than 3 scope in.
Be used for the polyolefin-wax dispersion of lubricant (A) and the weight average molecular weight range of modified polyolefin wax dispenser and be preferably 6000-15000.Preferred described weight-average molecular weight is not less than 6000, otherwise described lubricant is too soft, hinders the raising of described anti-continuous skimming wear.Preferred described weight-average molecular weight is not more than 15000, otherwise infringement resistance to compression system scratch property.
The weight average molecular weight range that is used for the polyolefin-wax dispersion of lubricant (B) is preferably 1000-5000.Preferred described weight-average molecular weight is not less than 1000, otherwise described lubricant will be tending towards experiencing thermolysis and described therein surface is exposed in nearly 1000 ℃ of pyritous convection drying process furnace, may total energy obtain enough lubricities.Described weight-average molecular weight preferably is not more than 5000, otherwise anti-continuous skimming wear decline.
Explain at the surface-treated metal plate of first aspect present invention the analytical procedure of the weight-average molecular weight of described polyolefin-wax dispersion and modified polyolefin wax dispenser and condition front.
As JIS K 5902 defineds, acid number (KOH-mg/g) scope that is used for the modified polyolefin wax dispenser of lubricant (A) is preferably 40 or lower.If acid number surpasses 40, then described lubricant hardening and can not obtain enough oilnesies.
The polyolefin-wax dispersion and the modified polyolefin wax dispenser that are used for lubricant (A) also preferably have 950-1000kg/m
3Density (as JIS K 6760 defineds), 0.2mm or lower hardness (acupuncture hardness) (as JIS K 2207 defineds), 80% or bigger degree of crystallinity (measuring) and 110-150 ℃ fusing point by X-ray diffraction.
Lubricant (A) and total content (B) are preferably the 1-30% weight of described water-based organic/inorganic composite coating by solid content.During less than 1% weight, can not obtain enough anti-continuous skimming wears, during greater than 30% weight, coating adhesion is poor.
The content of lubricant (A) with respect to lubricant (A) and total content (B) preferably in the scope of 10-90%.Less than 10% o'clock, can not improve the moving abradability of antiskid.Greater than 90% o'clock, resistance to compression system scratch property was than only making with lubricator (B) time difference.
The fraction of coverage scope of described water-based organic/inorganic composite membrane is 0.3-5.0g/m
2(pressing dry weight basis).More preferably 1.0-3.0g/m
2Preferred fraction of coverage is not less than 0.3g/m
2To realize the resistance to compression system scratch property of target, preferably be not more than 5.0g/m
2Be beneficial to weldability.
Forming the water-based organic/inorganic composite membrane of second aspect present invention used coating process, storing temperature and drying plant front explains at the formation of the water-based organic/inorganic composite membrane of first aspect present invention.
Then, according to third aspect present invention, on the upper strata of overlay metallization plate, form 0.05-0.3g/m
2Dry weight by one of water soluble resin and silicate compound or both and molecular weight be the water-based organic/inorganic composite membrane (C) formed of the lubricant (A) of the polyolefin-wax dispersion of 6000-15000 as the first layer, form 0.5-5.0g/m then
2The water-based organic/inorganic composite membrane of being made up of one of water soluble resin and silicate compound or both and colloidal silica (D) of dry weight is as the second layer, and the content of wherein said colloidal silica is counted 5-35% weight by solid content.
Fig. 3 illustrates first kind of embodiment according to the surface-treated metal plate of third aspect present invention, and Fig. 4 illustrates second kind of embodiment of surface-treated metal plate.
Among Fig. 3, has such structure according to first embodiment of the surface-treated metal plate of third aspect present invention: the first layer water-based organic/inorganic composite membrane (C) 22 and second layer water-based organic/inorganic composite membrane (D) 24 are arranged on overlay metallization plate 23.The first layer water-based organic/inorganic composite membrane (C) the 22nd, coating of being made up of one of water soluble resin and silicate compound or both and lubricant (A) and water by proper method coating (E) and baking form, and second layer water-based organic/inorganic composite membrane (D) the 24th is coated with the water-based organic/inorganic composite coating (F) be made up of one of water soluble resin and silicate compound or both and colloidal silica and water by proper method and also toasts and form.
Among Fig. 4, has such structure: the first layer water-based organic/inorganic composite membrane (C ') 22 and second layer water-based organic/inorganic composite membrane (D) 24 are arranged on overlay metallization plate 23 according to second embodiment of the surface-treated metal plate of third aspect present invention.The first layer water-based organic/inorganic composite membrane (C ') the 22nd, coating of being made up of one of water soluble resin and silicate compound or both and lubricant (A), lubricant (B) and water by the proper method coating (E) and baking form, and second layer water-based organic/inorganic composite membrane (D) the 24th is coated with the water-based organic/inorganic composite coating (F) be made up of one of water soluble resin and silicate compound or both and colloidal silica and water by proper method and also toasts and form.
Therefore, add polyolefin-wax dispersion that molecular weight transfers to appropriate value to form water-based organic/inorganic composite membrane (C) or (C '), on this film, form water-based organic/inorganic composite membrane (D) then as the upper strata, make described wax on the film surface of described water-based organic/inorganic composite membrane (D), protrude, control the hardness of wax and the avidity on film surface simultaneously with particle form.Also regulate the dioxide-containing silica of water-based organic/inorganic composite membrane (D), not only for the hardness of film but also for obtaining film properties such as solidity to corrosion and sticking power.Thereby can obtain not only to have satisfied solidity to corrosion and sticking power but also have the excellent resistance to compression system scratch property and the surface-treated metal plate of anti-Texturized property, kinetic friction coefficient is controlled at 0.07-0.15, static friction coefficient is controlled at 0.10 or higher, and prevents from pressing process to be broken away from by lubricant the generation of the adhering residue thing that film causes.
Explained later abrades the manufacture method of the surface-treated metal plate of property and anti-Texturized property excellence according to the resistance to compression system of third aspect present invention.This manufacture method is basic identical with the manufacture method according to the surface-treated metal plate of first aspect present invention, but institute's use organic/inorganic composite coating difference, and form two-layer water-based organic/inorganic composite membrane.
Be applicable to basic overlay metallization plate of the present invention as the front at as described in the surface-treated metal plate of first aspect.The coating fraction of coverage of every kind of overlay metallization plate is preferably every side 1g/m at least
2, because lower fraction of coverage causes solidity to corrosion to reduce.Form described water-based organic/inorganic composite membrane after can be before forming described water-based organic/inorganic composite membrane described overlay metallization plate being improved sticking power or corrosion proof base conditioning, also can be directly on without the overlay metallization plate of base conditioning the described water-based organic/inorganic composite membrane of formation.Described base conditioning there is not particular restriction, as long as can achieve the above object, but general preferred chromate treating, because it can improve solidity to corrosion or sticking power.Explain at the surface-treated metal plate of first aspect described chromic salt film and chromic salt fraction of coverage such as front.
As water soluble resin, can use the front at mentioned those of the surface-treated metal plate of first aspect.Be to obtain coating, described resin dispersion is become in the solvent to form emulsion at water, when needing, also can add various linking agents such as melamine resin or aminoresin.According to third aspect present invention, the water soluble resin that is used for the first layer more preferably is selected from the high-hydrophilic resin.As the resin that is used for the second layer, from performance and cost consideration, especially preferably use acrylic based resin such as olefin-acrylic multipolymer, under the situation of the violent press forming of needs, the preferred use demonstrates hardness and ductile ammonia ester-epoxy.
The silicate compound that is used for third aspect present invention and colloidal silica can described those be identical at the surface-treated metal plate of first aspect with the front.
Described colloidal silica adds in the described water-based organic/inorganic composite coating (F) with 5-35% weight by solid content.When being lower than 5% weight, can not obtain enough solidity to corrosions and resistance to compression system scratch property, and during greater than 35% weight, coating adhesion and resistance to compression system scratch property are relatively poor.
According to third aspect present invention, in described water-based organic/inorganic composite coating (E), lubricant of specified amount (A) or lubricant (A) and (B) and one of above-mentioned water soluble resin and silicate compound or both and colloidal silica and water be used in combination.Here, molecular weight be the polyolefin-wax dispersion of 6000-15000 as lubricant (A), molecular weight is that the polyolefin-wax dispersion of 1000-5000 is as lubricant (B).More preferably, with be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the modified polyolefin wax dispenser of 0.1-5.0 μ m as lubricant (A), be that 1000-5000 and granularity are that the polyolefin-wax dispersion of 0.1-3.0 μ m is as lubricant (B) with not polar functionalities, molecular weight.
As the polyolefin-wax dispersion, can use the polyethylene wax, Poly Propylene Wax or the polybutene wax that are substantially free of polar group at water or contain concentration and be not more than 5% emulsifying agent, preferably do not contain dispersion in the aqueous solution of emulsifying agent.
As the modified polyolefin wax dispenser, can use the polyethylene wax, Poly Propylene Wax or the polybutene wax that contain polar group at water or contain concentration and be not more than 5% emulsifying agent, preferably do not contain dispersion in the aqueous solution of emulsifying agent.Described polar group can be introduced (the polyene wax of oxidation) by with oxygenant such as oxygen, ozone, nitric acid etc. polyolefin-wax is carried out oxide treatment in the presence of catalyzer, also can by make ethylenic unsaturated carboxylic acid monomer such as vinylformic acid, methacrylic acid, Ba Dousuan, toxilic acid, fumaric acid, methylene-succinic acid etc. and polyolefin-wax be dissolved in the crude benzol etc., then nitrogen gas stream and polymerization starter (superoxide, redox agent, heavy metal catalyst etc.) down the heating grafting introduce.
The average particle size that is used for the polyolefin-wax dispersion of lubricant (A) and modified polyolefin wax dispenser is preferably 0.1-5.0 μ m, more preferably 1.0-4.0 μ m.Select the thickness of the granularity of lubricant (A) greater than the water-based organic/inorganic composite membrane (D) that forms as the upper strata.The average particle size of lubricant (A) preferably is not less than 0.1 μ m, otherwise is tending towards causing assembling and infringement stability.The average particle size of lubricant (A) also preferably is not less than the water-based organic/inorganic composite membrane (D) that forms as the upper strata, otherwise infringement resistance to compression system scratch property.In addition, described average particle size also preferably is not more than 5.0 μ m, otherwise the stability decreases of dispersion.The ratio of described average particle size and number average particle size preferably make average particle size/number average particle size less than 3 scope in.
The polyolefin-wax dispersion of lubricant (B) and the average particle size of modified polyolefin wax dispenser are preferably 0.1-3.0 μ m.Also select the thickness of the granularity of lubricant (B) greater than the water-based organic/inorganic composite membrane (D) that forms as the upper strata.Described average particle size preferably is not less than 0.1 μ m, otherwise is tending towards causing assembling and infringement stability.The average particle size of lubricant (B) also preferably is not more than 3.0 μ m or greater than the thickness of water-based organic/inorganic composite membrane (D), otherwise damages anti-Texturized property.
Be used for the polyolefin-wax dispersion of lubricant (A) and the weight-average molecular weight of modified polyolefin wax dispenser and be preferably 6000-15000.Preferred described weight-average molecular weight is not less than 6000, otherwise damages anti-Texturized property.Also preferred described weight-average molecular weight is not more than 15000, otherwise infringement resistance to compression system scratch property.
The weight average molecular weight range that is used for the polyolefin-wax dispersion of lubricant (B) is preferably 1000-5000.Preferred described weight-average molecular weight is not less than 1000, otherwise described lubricant will be tending towards experiencing thermolysis and described therein surface is exposed in nearly 1000 ℃ of pyritous convection drying process furnace, may total energy obtain enough lubricities.Described weight-average molecular weight also preferably is not more than 5000, otherwise can not reach by adding the effect that lubricant (B) further improves resistance to compression system scratch property.
Explain at the surface-treated metal plate of first aspect present invention the analytical procedure of the weight-average molecular weight of described polyolefin-wax dispersion and modified polyolefin wax dispenser and condition front.As JIS K 5902 defineds, acid number (KOH-mg/g) scope that is used for the modified polyolefin wax dispenser of lubricant (A) is preferably 40 or lower.If acid number surpasses 40, then described lubricant becomes too hard and can not obtain enough oilnesies.
The polyolefin-wax dispersion and the modified polyolefin wax dispenser that are used for lubricant (A) also preferably have 950-1000kg/m
3Density (as JIS K 6760 defineds), 0.2mm or lower hardness (acupuncture hardness) (as JIS K 2207 defineds), 80% or bigger degree of crystallinity (measuring) and 110-150 ℃ fusing point by X-ray diffraction.
The content of lubricant (A) or lubricant (A) and total content (B) are preferably the 2-60% weight of described water-based organic/inorganic composite coating by solid content.During less than 2% weight, can not obtain enough resistance to compression system scratch property, and during greater than 60% weight, coating adhesion is poor.
The fraction of coverage scope of described water-based organic/inorganic composite membrane (C) is 0.05-0.3g/m
2(pressing dry weight basis).More preferably 0.05-0.2g/m
2Preferred fraction of coverage is not less than 0.05g/m
2To realize the resistance to compression system scratch property of target, preferably be not more than 0.3g/m
2The formation that hinders upper layer film to prevent to reduce wettability.The fraction of coverage scope of described water-based organic/inorganic composite membrane (D) is 0.5-5.0g/m
2(pressing dry weight basis).More preferably 1.0-3.0g/m
2Preferred fraction of coverage is not less than 0.5g/m
2To realize target resistance to compression system scratch property, preferably be not more than 5.0g/m
2Be beneficial to weldability.
Forming the water-based organic/inorganic composite membrane of third aspect present invention used coating process, storing temperature and drying plant front explains at the formation of the water-based organic/inorganic composite membrane of first aspect present invention.
Kinetic friction coefficient according to the surface-treated metal plate surface of third aspect present invention is preferably 0.07-0.15, and static friction coefficient is preferably 0.10 or higher.Kinetic friction coefficient is higher than at 0.15 o'clock, and resistance to compression system scratch property is poor, and kinetic friction coefficient be lower than 0.07 or static friction coefficient be lower than at 0.10 o'clock, anti-Texturized property is poor.
Embodiment
Explain the present invention in more detail below by embodiment and Comparative Examples, should understand the present invention and limited by these embodiment.
At first, explanation is according to the embodiment of first aspect present invention.
(1) types of agents
The tabulation of agents useful for same is shown in Table 1.All polyolefin-wax dispersions except that D1 and D8 all have 950-1000kg/m
3Density (as JIS K 6760 defineds), 0.2mm or lower hardness (acupuncture hardness) (as JIS K 2207 defineds), 80% or bigger degree of crystallinity (measuring) and 110-150 ℃ fusing point by X-ray diffraction.
The tabulation of table 1 reagent
| Reagent | Number | Name of product |
| Organic resin | A1 | Acrylic resin (AP-1508 (12), Toa Gosei Co., Ltd.) |
| A2 | Polyolefin-based water soluble resin (AR-2300, Toho Chemical Industry Co., Ltd.) | |
| A3 | The polyurethane-base water soluble resin (RA-85, Nippon-NSC) | |
| A4 | Epoxy group(ing) water soluble resin (DICFINE EM-60, Dainippon Ink and Chemicals Inc.) | |
| Silicate compound | B1 | Lithium silicate |
| B2 | Water glass | |
| B3 | Potassium silicate | |
| Colloidal silica | C1 | Aqueous colloidal silica (SNOWTEX N, Nissan Chemical Industries, Ltd.) |
| C2 | Aqueous colloidal silica (SNOWTEX UP, Nissan Chemical Industries, Ltd.) | |
| The polyolefin-wax dispersion | D1 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 3.0 μ m) |
| D2 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 3.0 μ m) | |
| D3 | Polyethylene (molecular weight: 8000, acid number: 0, granularity: 3.0 μ m) | |
| D4 | Polyethylene (molecular weight: 15000, acid number: 0, granularity: 3.0 μ m) | |
| D5 | Polyethylene (molecular weight: 20000, acid number: 0, granularity: 3.0 μ m) | |
| D6 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 0.1 μ m) | |
| D7 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 5.0 μ m) | |
| D8 | Modified poly ethylene (molecular weight: 1000, acid number: 20, granularity: 1.0 μ m) | |
| D9 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 1.0 μ m) | |
| D10 | Modified poly ethylene (molecular weight: 8000, acid number: 20, granularity: 1.0 μ m) | |
| D11 | Modified poly ethylene (molecular weight: 15000, acid number: 20, granularity: 1.0 μ m) | |
| D12 | Modified poly ethylene (molecular weight: 20000, acid number: 20, granularity: 1.0 μ m) | |
| D13 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 0.1 μ m) | |
| D14 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 5.0 μ m) | |
| D15 | Modified poly ethylene (molecular weight: 6000, acid number: 40, granularity: 1.0 μ m) | |
| D16 | Modified poly ethylene (molecular weight: 6000, acid number: 100, granularity: 1.0 μ m) |
(2) type of metal sheet
Used metal sheet is shown in Table 2.
The type of table 2 metal sheet and coating fraction of coverage (thickness of slab: 0.8mm)
| Abbreviation | The type of metal sheet |
| ????EG | The steel plate of electro-galvanizing (coating fraction of coverage: 20g/m 2) |
| ????ZN | The steel plate of electro-galvanizing-nickel (coating fraction of coverage: 20g/m 2, nickel content: 12 weight %) |
| ????GI | The steel plate of galvanizing (coating fraction of coverage: 60g/m 2) |
(3) chromate treating
By contain 50g/l chromic acid and 0.3g/l vitriolic bathe in 10A/dm
2Current density conduction regulation electric weight make EG in the table 2 and ZN stand electrolytic chromate to handle, after the washing, dry under 80 ℃ peak value metal temperature with hot-air drying stove.
With containing the also SiO of ortho-chromic acid and silicon-dioxide of 40% reductive
2/ CrO
3Than being GI in 3 the chromate treating liquid coating table 2, dry under the situation of not washing then.
Determine chromate film fraction of coverage (by Cr) by fluorescent X-ray analysis.
(4) preparation of water-based organic/inorganic composite coating
Make one of the water soluble resin shown in the table 1 and silicate compound or both, colloidal silica and polyolefin-wax dispersion prepare water-based organic/inorganic composite coating by table 4 to mixed shown in 6.
(5) coating of water-based organic/inorganic composite coating and drying
The water-based organic/inorganic composite coating for preparing in above (4) is applied to passing through of obtaining in above (3) reaches listed dry weight among the table 4-6 on the overlay metallization plate of chromate treating, baking and dry under 140 ℃ peak value metal temperature is made sample and is used for estimating.Calculate the fraction of coverage of organic hybrid films according to the measurement of liquid film weight in the coating process.
(6) performance evaluation
A. the solidity to corrosion of plate
By preparation in salt spray testing described in the JIS Z 2371 test above (5) respectively estimate sample, wherein on the steel plate sample after under 35 ℃ the atmosphere temperature 5%NaCl aqueous solution being sprayed onto coating, the generation of measuring white rust after 72 hours.◎ and zero opinion rating are judged to be satisfaction in the following evaluation criteria.
◎: no white rust
Zero: white rust less than 10%
△: 〉=10% and＜50% white rust
*: 〉=50% white rust
B. the solidity to corrosion behind the Sven-Gan Eriksson cut (Erichsen drawing)
What make preparation in above (5) respectively estimates the Sven-Gan Eriksson cut that sample stands 6mm, then on the steel plate sample after under 35 ℃ the atmosphere temperature 5%NaCl aqueous solution being sprayed onto coating, and the generation of measuring white rust in the described scored area after 48 hours.◎ and zero opinion rating are judged to be satisfaction in the following evaluation criteria.
◎: no white rust
Zero: white rust less than 5%
△: 〉=5% and＜20% white rust
*: 〉=20% white rust
C. coating adhesion
(Amilack#1000, Kansai Paint Co. Ltd.) to the dried film thickness of 25 μ m, toast described dry film 20 minutes under 130 ℃ furnace temperature to be coated with melamine-phthalic resin coating on the sample with respectively estimating of preparing in above (5) of scraping strip coating machine.After the standing over night, the Sven-Gan Eriksson cut that makes in the boiling water sample that soaks 30 minutes and another unsoaked sample all stand 7mm is attached to sealing tape (ProductName: Cellotape, Nichiban Co., the product of Ltd.) in the Sven-Gan Eriksson cut district of each sample.Tear described sealing tape 45 ° diagonal fast, the outward appearance in the described Sven-Gan Eriksson cut of visual assessment district.◎ and zero opinion rating are judged to be satisfaction in the following evaluation criteria.
◎: do not have and peel off
Zero: the area of peeling off less than 5%
△: 〉=5% and＜50% peel off area
*: 〉=50% peel off area
D. continuous welding
Make each sample of preparation in above (5) stand the series spot welding test under condition shown in the table 3, measuring and firmly forming nugget size is 3mm or bigger number of welds.
Table 3 welding conditions
| Parameter | Condition |
| Welding current | ????8500A |
| Duration of charging | 10 cycles (50Hz) |
| Electrode diameter | ????4.5mm |
| Electrode force | ????200kgf |
◎ and zero opinion rating are judged to be satisfaction in the following evaluation criteria.
◎: solder joint: 〉=5000
Zero: solder joint: 〉=2500 and＜5000
△: solder joint: 〉=1000 and＜2500
*: solder joint:＜1000
E. resistance to compression system abrades property
Make each sample of preparation in above (5) stand the rectangular drawing test.The condition of described rectangular drawing test is that blank folding power is 6 tons, and (0.8 * 220 * 180mm) is molded into 65 * 115mm and high 50mm, visual assessment sliding surface after the mold pressing with sample.◎ and zero opinion rating are judged to be satisfaction in the following evaluation criteria.
◎: less than defective due to scratch
Zero: because of defective due to scratch and the slip scratch on less than 50% sliding area area
△: because of the scratch and the slip scratch due to defective at least 50% sliding area area
*: expose following metal, scratch
F. abrasion resistance test
Make each sample of preparation in above (5) pass through the Vinylite film at 10g/cm
2Load under stand per minute 360 times the ellipse swing in sliding area, produce wearing and tearing.Test after 10 minutes the visual assessment specimen surface.◎ and zero opinion rating are judged to be satisfaction in the following evaluation criteria.
◎: less than defective due to scratch
Zero: because of defective due to scratch and the slip scratch on less than 50% sliding area area
△: because of the scratch and the slip scratch due to defective at least 50% sliding area area
*: expose following metal
G. static friction coefficient
Make 25cm
2Each sample of preparation is installed on the testing tool of plane in above (5) of removing deburring of area, with Shinto Scientific Co., the 10D HEIDON static friction coefficient measuring apparatus that Ltd. provides is being measured static friction coefficient with 0.5 °/second between the sample of preparation under the condition of 200g load in above (5).
H. kinetic friction coefficient
With Shinto Scientfic Co., the kinetic friction coefficient of each sample of preparation in (5) more than the 14S HEIDON dynamic friction coefficient measuring device that Ltd. provides is measured under the condition of the slip of 10mm diameter Stainless Steel Ball, 100g load and 150mm/ minute sliding velocity.
I. anti-Texturized property
Make several have the internal diameter 508mm of different coefficients of friction, the 10t coiled materials of thickness of slab 1mm, after every volume usefulness crane lifting 3 times, measurement is checked the relation of mobile degree and kinetic friction coefficient and static friction coefficient because of the mobile degree (distance) of coiled material coiling direction (vertically) tip of the loose generation of outmost turns.Found that between kinetic friction coefficient, static friction coefficient and the mobile degree (distance) interrelated well because of coiling direction (vertically) the coiled material end of the loose generation of reeling.Kinetic friction coefficient less than 0.07 and static friction coefficient less than 0.10 o'clock, because of reel loose due to the coiled material tip displacement surpass 50mm, but kinetic friction coefficient be 0.07 or bigger and static friction coefficient be 0.10 or when bigger, because of reel loose due to the coiled material tip displacement successfully be limited in less than 30mm.Thereby, in this laboratory test, with above by " g " and " h " measurement static friction coefficient and kinetic friction coefficient as the indication of anti-Texturized property.Zero opinion rating is judged to be satisfaction in the following evaluation criteria.
Zero: kinetic friction coefficient: 〉=0.07, static friction coefficient: 〉=0.1
*: kinetic friction coefficient:＜0.07, static friction coefficient:＜0.1
Evaluation result is shown in table 7 in 9.These results clearly prove, technology of the present invention can be produced the performance with excellence and be comprised that solidity to corrosion, sticking power and weldability and excellent resistance to compression system abrade the surface-treated metal plate of property and anti-Texturized property, the kinetic friction coefficient of wherein said metal sheet surface is controlled at 0.07-0.15, and static friction coefficient is controlled at 0.1 or higher.
Table 4
| Number | Metal sheet | Cr fraction of coverage (mg/m 2) | The organic/inorganic composite membrane | ||||||||||
| Water soluble resin/silicate compound 1) | Silicon-dioxide 2) | Wax 3) | Fraction of coverage (g/m 2) | ||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | ||||
| ????1 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D1 | ????10 | ??- | ????- | ????1.0 |
| ????2 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D2 | ????10 | ??- | ????- | ????1.0 |
| ????3 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D3 | ????10 | ??- | ????- | ????1.0 |
| ????4 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D4 | ????10 | ??- | ????- | ????1.0 |
| ????5 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D5 | ????10 | ??- | ????- | ????1.0 |
| ????6 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D6 | ????10 | ??- | ????- | ????1.0 |
| ????7 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D7 | ????10 | ??- | ????- | ????1.0 |
| ????8 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D8 | ????10 | ??- | ????- | ????1.0 |
| ????9 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D9 | ????10 | ??- | ????- | ????1.0 |
| ????10 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D10 | ????10 | ??- | ????- | ????1.0 |
| ????11 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D11 | ????10 | ??- | ????- | ????1.0 |
| ????12 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D12 | ????10 | ??- | ????- | ????1.0 |
| ????13 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D13 | ????10 | ??- | ????- | ????1.0 |
| ????14 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D14 | ????10 | ??- | ????- | ????1.0 |
| ????15 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D15 | ????10 | ??- | ????- | ????1.0 |
| ????16 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D16 | ????10 | ??- | ????- | ????1.0 |
| ????17 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D3 | ????1 | ??- | ????- | ????1.0 |
| ????18 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D3 | ????6 | ??- | ????- | ????1.0 |
| ????19 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D3 | ????30 | ??- | ????- | ????1.0 |
| ????20 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D4 | ????1 | ??- | ????- | ????1.0 |
| ????21 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D4 | ????6 | ??- | ????- | ????1.0 |
| ????22 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D4 | ????30 | ??- | ????- | ????1.0 |
| ????23 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D9 | ????1 | ??- | ????- | ????1.0 |
| ????24 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D9 | ????6 | ??- | ????- | ????1.0 |
| ????25 | ????EG | ????40 | ????A1 | ????100 | ??- | ????- | ????C1 | ????15 | ????D9 | ????30 | ??- | ????- | ????1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silicon-dioxide that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 5
| Number | Metal sheet | Cr fraction of coverage (mg/m 2) | The organic/inorganic composite membrane | ||||||||||
| Water soluble resin/silicate compound 1) | Silicon-dioxide 2) | Wax 3) | Fraction of coverage (g/m 2) | ||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | ||||
| ??26 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D2 | ????5 | ????D4 | ????5 | ????1.0 |
| ??27 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D2 | ????5 | ????D9 | ????5 | ????1.0 |
| ??28 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D3 | ????10 | ????- | ????- | ????0.1 |
| ??29 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????03 | ????10 | ????- | ????- | ????0.3 |
| ??30 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D3 | ????10 | ????- | ????- | ????2.0 |
| ??31 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D3 | ????10 | ????- | ????- | ????5.0 |
| ??32 | ??EC | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D3 | ????10 | ????- | ????- | ????10.0 |
| ??33 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D4 | ????10 | ????- | ????- | ????0.1 |
| ??34 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D4 | ????10 | ????- | ????- | ????0.3 |
| ??35 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D4 | ????10 | ????- | ????- | ????2.0 |
| ??36 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D4 | ????10 | ????- | ????- | ????5.0 |
| ??37 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D4 | ????10 | ????- | ????- | ????10.0 |
| ??38 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D9 | ????10 | ????- | ????- | ????0.1 |
| ??39 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D9 | ????10 | ????- | ????- | ????0.3 |
| ??40 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D9 | ????10 | ????- | ????- | ????2.0 |
| ??41 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D9 | ????10 | ????- | ????- | ????5.0 |
| ??42 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????15 | ????D9 | ????10 | ????- | ????- | ????10.0 |
| ??43 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????0 | ????D3 | ????10 | ????- | ????- | ????1.0 |
| ??44 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????5 | ????D3 | ????10 | ????- | ????- | ????1.0 |
| ??45 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????10 | ????D3 | ????10 | ????- | ????- | ????1.0 |
| ??46 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????35 | ????D3 | ????10 | ????- | ????- | ????1.0 |
| ??47 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C1 | ????50 | ????D3 | ????10 | ????- | ????- | ????1.0 |
| ??48 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C2 | ????0 | ????D4 | ????10 | ????- | ????- | ????1.0 |
| ??49 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C2 | ????5 | ????D4 | ????10 | ????- | ????- | ????1.0 |
| ??50 | ??EG | ????40 | ????A1 | ????100 | ???- | ??- | ????C2 | ????10 | ????D4 | ????10 | ????- | ????- | ????1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silicon-dioxide that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 6
| Number | Metal sheet | Cr fraction of coverage (mg/m 2) | The organic/inorganic composite membrane | ||||||||||
| Water soluble resin/silicate compound 1) | Silicon-dioxide 2) | Wax 3) | Fraction of coverage (g/m 2) | ||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | ||||
| ??51 | ??EG | ????40 | ??A1 | ????100 | ????- | ????- | ????C2 | ????35 | ????D4 | ????10 | ????- | ??- | ????1.0 |
| ??52 | ??EG | ????40 | ??A1 | ????100 | ????- | ????- | ????C2 | ????50 | ????D4 | ????10 | ????- | ??- | ????1.0 |
| ??53 | ??EG | ????40 | ??A2 | ????90 | ????A4 | ????10 | ????C1 | ????15 | ????D3 | ????10 | ????- | ??- | ????1.0 |
| ??54 | ??EG | ????40 | ??A2 | ????90 | ????A4 | ????10 | ????C1 | ????15 | ????D4 | ????10 | ????- | ??- | ????1.0 |
| ??55 | ??EG | ????40 | ??A2 | ????90 | ????A4 | ????10 | ????C1 | ????15 | ????D9 | ????10 | ????- | ??- | ????1.0 |
| ??56 | ??EG | ????40 | ??A3 | ????90 | ????A4 | ????10 | ????C1 | ????15 | ????D3 | ????10 | ????- | ??- | ????1.0 |
| ??57 | ??EG | ????40 | ??A3 | ????90 | ????A4 | ????10 | ????C1 | ????15 | ????D4 | ????10 | ????- | ??- | ????1.0 |
| ??58 | ??EG | ????40 | ??A3 | ????90 | ????A4 | ????10 | ????C1 | ????15 | ????D9 | ????10 | ????- | ??- | ????1.0 |
| ??59 | ??EG | ????40 | ??B1 | ????100 | ????- | ????- | ????C1 | ????15 | ????D3 | ????10 | ????- | ??- | ????1.0 |
| ??60 | ??EG | ????40 | ??B2 | ????100 | ????- | ????- | ????C1 | ????15 | ????D3 | ????10 | ????- | ??- | ????1.0 |
| ??61 | ??EG | ????40 | ??B3 | ????100 | ????- | ????- | ????C1 | ????15 | ????D3 | ????10 | ????- | ??- | ????1.0 |
| ??62 | ??EG | ????40 | ??B1 | ????90 | ????A1 | ????10 | ????C1 | ????15 | ????D3 | ????10 | ????- | ??- | ????1.0 |
| ??63 | ??EG | ????40 | ??B1 | ????90 | ????A4 | ????10 | ????C1 | ????15 | ????D3 | ????10 | ????- | ??- | ????1.0 |
| ??64 | ??EG | ????- | ??A3 | ????90 | ????A4 | ????10 | ????C1 | ????15 | ????D3 | ????10 | ????- | ??- | ????1.0 |
| ??65 | ??EG | ????- | ??A3 | ????90 | ????A4 | ????10 | ????C1 | ????15 | ????D4 | ????10 | ????- | ??- | ????1.0 |
| ??66 | ??EG | ????- | ??A3 | ????90 | ????A4 | ????10 | ????C1 | ????15 | ????D9 | ????10 | ????- | ??- | ????1.0 |
| ??67 | ??ZN | ????40 | ??A3 | ????90 | ????A4 | ????10 | ????C1 | ????15 | ????D3 | ????10 | ????- | ??- | ????1.0 |
| ??68 | ??GI | ????40 | ??A3 | ????90 | ????A4 | ????10 | ????C1 | ????15 | ????D3 | ????10 | ????- | ??- | ????1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silicon-dioxide that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 7
| Number | Performance | Note | |||||||||
| Dull and stereotyped solidity to corrosion | Solidity to corrosion behind the Sven-Gan Eriksson cut | Coating adhesion | Weldability | Resistance to compression system scratch property | Abrasion resistance | Anti-Texturized property | Kinetic friction coefficient | Static friction coefficient | |||
| Do not soak | Soak | ||||||||||
| 1 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????× | ????0.05 | ????0.07 | Comparative Examples |
| 2 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.07 | ????0.15 | The present invention |
| 3 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.20 | The present invention |
| 4 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????0.15 | ????0.25 | The present invention |
| 5 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????△ | ????○ | ????○ | ????0.20 | ????0.30 | Comparative Examples |
| 6 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????0.08 | ????0.15 | The present invention |
| 7 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.07 | ????0.12 | The present invention |
| 8 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????× | ????0.06 | ????0.10 | Comparative Examples |
| 9 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.09 | ????0.20 | The present invention |
| 10 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.25 | The present invention |
| 11 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| 12 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????× | ????△ | ????○ | ????0.20 | ????0.35 | Comparative Examples |
| 13 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????0.08 | ????0.20 | The present invention |
| 14 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.07 | ????0.17 | The present invention |
| 15 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.15 | ????0.30 | The present invention |
| 16 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????× | ????× | ????○ | ????0.20 | ????0.35 | The present invention |
| 17 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| 18 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.25 | The present invention |
| 19 | ????○ | ????○ | ????○ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????0.08 | ????0.15 | The present invention |
| 20 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| 21 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????0.15 | ????0.30 | The present invention |
| 22 | ????○ | ????○ | ????○ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????0.08 | ????0.15 | The present invention |
| 23 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| 24 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????0.15 | ????0.30 | The present invention |
| 25 | ????○ | ????○ | ????○ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????0.08 | ????0.15 | The present invention |
Table 8
| Number | Performance | Note | |||||||||
| Dull and stereotyped solidity to corrosion | Solidity to corrosion behind the Sven-Gan Eriksson cut | Coating adhesion | Weldability | Resistance to compression system is wiped anti-property | Abrasion resistance | Anti-Texturized property | Kinetic friction coefficient | Static friction coefficient | |||
| Do not soak | Soak | ||||||||||
| 26 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.07 | ????0.15 | The present invention |
| 27 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.07 | ????0.18 | The present invention |
| 28 | ????× | ????× | ????△ | ????△ | ????◎ | ????× | ????× | ????○ | ????0.25 | ????0.40 | Comparative Examples |
| 29 | ????○ | ????○ | ????○ | ????○ | ????◎ | ????○ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| 30 | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.20 | The present invention |
| 31 | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.20 | The present invention |
| 32 | ????◎ | ????◎ | ????◎ | ????○ | ????× | ????◎ | ????◎ | ????○ | ????0.10 | ????0.20 | Comparative Examples |
| 33 | ????× | ????× | ????△ | ????△ | ????◎ | ????× | ????× | ????○ | ????0.25 | ????0.45 | Comparative Examples |
| 34 | ????○ | ????○ | ????○ | ????○ | ????◎ | ????○ | ????○ | ????○ | ????0.15 | ????0.35 | The present invention |
| 35 | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????○ | ????0.15 | ????0.25 | The present invention |
| 36 | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.20 | The present invention |
| 37 | ????◎ | ????◎ | ????◎ | ????○ | ????× | ????◎ | ????◎ | ????○ | ????0.10 | ????0.20 | Comparative Examples |
| 38 | ????× | ????× | ????△ | ????△ | ????◎ | ????× | ????× | ????○ | ????0.25 | ????0.45 | Comparative Examples |
| 39 | ????○ | ????○ | ????○ | ????○ | ????◎ | ????○ | ????○ | ????○ | ????0.15 | ????0.35 | The present invention |
| 40 | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????○ | ????0.09 | ????0.20 | The present invention |
| 41 | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????◎ | ????◎ | ????○ | ????0.09 | ????0.20 | The present invention |
| 42 | ????◎ | ????◎ | ????◎ | ????○ | ????× | ????◎ | ????◎ | ????○ | ????0.09 | ????0.20 | Comparative Examples |
| 43 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????△ | ????○ | ????○ | ????0.10 | ????0.20 | Comparative Examples |
| 44 | ????○ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| 45 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.20 | The present invention |
| 46 | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.20 | The present invention |
| 47 | ????○ | ????○ | ????○ | ????△ | ????○ | ????△ | ????○ | ????○ | ????0.10 | ????0.20 | Comparative Examples |
| 48 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????△ | ????○ | ????○ | ????0.15 | ????0.25 | Comparative Examples |
| 49 | ????○ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????0.15 | ????0.25 | The present invention |
| 50 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.15 | ????0.25 | The present invention |
Table 9
| Number | Performance | Note | |||||||||
| Dull and stereotyped solidity to corrosion | Solidity to corrosion behind the Sven-Gan Eriksson cut | Coating adhesion | Weldability | Resistance to compression system scratch property | Abrasion resistance | Anti-Texturized property | Kinetic friction coefficient | Static friction coefficient | |||
| Do not soak | Soak | ||||||||||
| 51 | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????0.15 | ????0.25 | The present invention |
| 52 | ????○ | ????○ | ????○ | ????△ | ????○ | ????△ | ????○ | ????○ | ????0.15 | ????0.25 | Comparative Examples |
| 53 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.15 | The present invention |
| 54 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????0.15 | ????0.20 | The present invention |
| 55 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.09 | ????0.15 | The present invention |
| 56 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.20 | The present invention |
| 57 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????0.15 | ????0.25 | The present invention |
| 58 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.09 | ????0.20 | The present invention |
| 59 | ????◎ | ????○ | ????○ | ????△ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.25 | The present invention |
| 60 | ????◎ | ????○ | ????○ | ????△ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.25 | The present invention |
| 61 | ????◎ | ????○ | ????○ | ????△ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.25 | The present invention |
| 62 | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.25 | The present invention |
| 63 | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.25 | The present invention |
| 64 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.20 | The present invention |
| 65 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????○ | ????◎ | ????○ | ????0.15 | ????0.25 | The present invention |
| 66 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????0.09 | ????0.20 | The present invention |
| 67 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.20 | The present invention |
| 68 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????0.10 | ????0.20 | The present invention |
Explained later is according to the embodiment of second aspect present invention.
(1) types of agents
The tabulation of agents useful for same is shown in Table 10.All lubricants (A) except that D7 all have 950-1000kg/m
3Density (as JIS K 6760 defineds), 0.2mm or lower hardness (acupuncture hardness) (as JIS K 2207 defineds), 80% or bigger degree of crystallinity (measuring) and 110-150 ℃ fusing point by X-ray diffraction.
The tabulation of table 10 reagent
| Reagent | Number | Name of product |
| Organic resin | A1 | Acrylic resin (AP-1508 (12), Toa Gosei Co., Ltd.) |
| A2 | Polyolefin-based water soluble resin (AR-2300, Toho Chemical Industry Co., Ltd.) | |
| A3 | The polyurethane-base water soluble resin (RA-85, Nippon-NSC) | |
| A4 | Epoxy group(ing) water soluble resin (DICFINE EM-60, Dainippon Ink and Chemicals Inc.) | |
| Silicate compound | B1 | Lithium silicate |
| B2 | Water glass | |
| B3 | Potassium silicate | |
| Colloidal silica | C1 | Aqueous colloidal silica (SNOWTEX N, Nissan Chemical Industries, Ltd.) |
| C2 | Aqueous colloidal silica (SNOWTEX UP, Nissan Chemical Industries, Ltd.) | |
| Lubricant A﹠ contrast | D1 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 3.0 μ m) |
| D2 | Polyethylene (molecular weight: 8000, acid number: 0, granularity: 3.0 μ m) | |
| D3 | Polyethylene (molecular weight: 15000, acid number: 0, granularity: 3.0 μ m) | |
| D4 | Polyethylene (molecular weight: 20000, acid number: 0, granularity: 3.0 μ m) | |
| D5 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 0.1 μ m) | |
| D6 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 5.0 μ m) | |
| D7 | Modified poly ethylene (molecular weight: 1000, acid number: 20, granularity: 1.0 μ m) | |
| D8 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 1.0 μ m) | |
| D9 | Modified poly ethylene (molecular weight: 8000, acid number: 20, granularity: 1.0 μ m) | |
| D10 | Modified poly ethylene (molecular weight: 15000, acid number: 20, granularity: 1.0 μ m) | |
| D11 | Modified poly ethylene (molecular weight: 20000, acid number: 20, granularity: 1.0 μ m) | |
| D12 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 0.1 μ m) | |
| D13 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 5.0 μ m) | |
| D14 | Modified poly ethylene (molecular weight: 6000, acid number: 40, granularity: 1.0 μ m) | |
| D15 | Modified poly ethylene (molecular weight: 6000, acid number: 100, granularity: 1.0 μ m) | |
| Lubricant B﹠ contrast | E16 | Polyethylene (molecular weight: 500, acid number: 0, granularity: 3.0 μ m) |
| E17 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 3.0 μ m) | |
| E18 | Polyethylene (molecular weight: 5000, acid number: 0, granularity: 3.0 μ m) | |
| E19 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 5.0 μ m) | |
| E20 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 0.1 μ m) | |
| E21 | Polyethylene (molecular weight: 5500, acid number: 0, granularity: 3.0 μ m) |
(2) type of metal sheet
Used metal sheet is listed those in the table 2.
(3) chromate treating
The carrying out of explaining at first aspect as the front.
(4) preparation of water-based organic/inorganic composite coating
Make from one of the water soluble resin of table 10 and silicate compound or both, colloidal silica and lubricant and prepare water-based organic/inorganic composite coating with table 11 to mixed shown in 13.
(5) coating of water-based organic/inorganic composite coating and drying
The water-based organic/inorganic composite coating of preparation in above (4) is applied on the overlay metallization plate of the chromate treating that obtains in above (3) and reaches listed dry weight among the table 11-13, baking and dry in the heat-wind circulate drying stove under the peak value metal temperature of 500 ℃ atmosphere temperatures and 140 ℃ is made sample and is used for estimating.Calculate the fraction of coverage of organic hybrid films according to the measurement of liquid film weight in the coating process.
(6) performance evaluation
A. the solidity to corrosion of plate
To estimate at the mode of being explained according to the embodiment of first aspect.
B. the solidity to corrosion behind the Sven-Gan Eriksson cut
To estimate at the mode of being explained according to the embodiment of first aspect.
C. coating adhesion
To estimate at the mode of being explained according to the embodiment of first aspect.
D. continuous welding
To estimate at the mode of being explained according to the embodiment of first aspect.
E. resistance to compression system abrades property
To estimate at the mode of being explained according to the embodiment of first aspect.
F. abrasion resistance test
To estimate at the mode of being explained according to the embodiment of first aspect.
G. anti-continuous skimming wear
The plastics (video cassette) that 10mm is stamped out are fixed in the end of 500g load in the rotary type sliding wear testing instrument, are placed on then on the specimen surface of having made disk.Change the observation specimen surface with 60 rev/mins of every rotations 50, estimate the revolution when scratch occurring in the coating.
H. kinetic friction coefficient
To estimate at the mode of being explained according to the embodiment of first aspect.
I. thermolysis stability
Each sample that makes preparation in above (5) is heat-treated under the peak value metal temperature of air ratio at 140 ℃ of 900 ℃ atmosphere temperature and 1.0-1.5 in the convection drying process furnace, resistance to compression system scratch property and anti-continuous skimming wear reduction if kinetic friction coefficient is higher, then be evaluated as dissatisfied (*), be evaluated as satisfied (zero) if they are constant.
Zero: the kinetic friction coefficient after the thermal treatment, resistance to compression system scratch property and anti-continuous skimming wear are constant
*: the higher and resistance to compression system of the kinetic friction coefficient after thermal treatment scratch property and anti-continuous skimming wear reduction
Evaluation result is shown in table 14 in 16.These results prove that clearly technology of the present invention can be produced has the surface-treated metal plate that excellent performance comprises the resistance to compression system scratch property of solidity to corrosion, sticking power and weldability and excellence and resists continuous skimming wear.
Table 11
| Number | Metal sheet | Cr fraction of coverage (mg/m 2) | The organic/inorganic composite membrane | ||||||||||||
| Water soluble resin/silicate compound 1) | Silicon-dioxide 2) | Lubricant (A) 3) | Lubricant (B) 3) | Fraction of coverage (g/m 2) | |||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | ||||
| ??1 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D1 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??2 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??3 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??4 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D4 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??5 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D5 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??6 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D6 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??7 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D7 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??8 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D8 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??9 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??10 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D10 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??11 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D11 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??12 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D12 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??13 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D13 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??14 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D14 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??15 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D15 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??16 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E16 | ????5 | ????1.0 |
| ??17 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E18 | ????5 | ????1.0 |
| ??18 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E19 | ????5 | ????1.0 |
| ??19 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E20 | ????5 | ????1.0 |
| ??20 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E21 | ????5 | ????1.0 |
| ??21 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E16 | ????5 | ????1.0 |
| ??22 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E18 | ????5 | ????1.0 |
| ??23 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E19 | ????5 | ????1.0 |
| ??24 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E20 | ????5 | ????1.0 |
| ??25 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E21 | ????5 | ????1.0 |
| ??26 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E16 | ????5 | ????1.0 |
| ??27 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E18 | ????5 | ????1.0 |
| ??28 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E19 | ????5 | ????1.0 |
| ??29 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E20 | ????5 | ????1.0 |
| ??30 | ????EG | ????40 | ????A1 | ??100 | ????- | ????- | ????C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E21 | ????5 | ????1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silicon-dioxide that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 12
| Number | Metal sheet | Cr fraction of coverage (mg/m 2) | The organic/inorganic composite membrane | ||||||||||||
| Water soluble resin/silicate compound 1) | Silicon-dioxide 2) | Lubricant (A) 3) | Lubricant (B) 3) | Fraction of coverage (g/m 2) | |||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | ||||
| ??31 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????1 | ??- | ????- | ??E17 | ????9 | ????1.0 |
| ??32 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????9 | ??- | ????- | ??E17 | ????1 | ????1.0 |
| ??33 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D3 | ????1 | ??- | ????- | ??E17 | ????9 | ????1.0 |
| ??34 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D3 | ????9 | ??- | ????- | ??E17 | ????1 | ????1.0 |
| ??35 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????2.5 | ??D8 | ????2.5 | ??E17 | ????5 | ????1.0 |
| ??36 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D3 | ????2.5 | ??D8 | ????2.5 | ??E17 | ????5 | ????1.0 |
| ??37 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????0.5 | ??- | ????- | ??E17 | ????0.5 | ????1.0 |
| ??38 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????3.0 | ??- | ????- | ??E17 | ????3 | ????1.0 |
| ??39 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????15.0 | ??- | ????- | ??E17 | ????15 | ????1.0 |
| ??40 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D3 | ????0.5 | ??- | ????- | ??E17 | ????0.5 | ????1.0 |
| ??41 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D3 | ????3.0 | ??- | ????- | ??E17 | ????3 | ????1.0 |
| ??42 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D3 | ????15.0 | ??- | ????- | ??E17 | ????15 | ????1.0 |
| ??43 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????0.1 |
| ??44 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????0.3 |
| ??45 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????2.0 |
| ??46 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????5.0 |
| ??47 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????10.0 |
| ??48 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E17 | ????5 | ????0.1 |
| ??49 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E17 | ????5 | ????0.3 |
| ??50 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E17 | ????5 | ????2.0 |
| ??51 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E17 | ????5 | ????5.0 |
| ??52 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E17 | ????5 | ????10.0 |
| ??53 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E17 | ????5 | ????0.1 |
| ??54 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E17 | ????5 | ????0.3 |
| ??55 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E17 | ????5 | ????2.0 |
| ??56 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E17 | ????5 | ????5.0 |
| ??57 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E17 | ????5 | ????10.0 |
| ??58 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????0 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??59 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????5 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??60 | ????EG | ????40 | ??A1 | ????100 | ????- | ????- | ??C1 | ????10 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silicon-dioxide that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 13
| Number | Metal sheet | Cr fraction of coverage (mg/m 2) | The organic/inorganic composite membrane | ||||||||||||
| Water soluble resin/silicate compound 1) | Silicon-dioxide 2) | Lubricant (A) 3) | Lubricant (B) 3) | Fraction of coverage (g/m 2) | |||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | ||||
| ??61 | ????EG | ????40 | ????A1 | ????100 | ????- | ????- | ??C1 | ????35 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??62 | ????EG | ????40 | ????A1 | ????100 | ????- | ????- | ??C1 | ????50 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??63 | ????EG | ????40 | ????A1 | ????100 | ????- | ????- | ??C2 | ????0 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??64 | ????EG | ????40 | ????A1 | ????100 | ????- | ????- | ??C2 | ????5 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??65 | ????EG | ????40 | ????A1 | ????100 | ????- | ????- | ??C2 | ????10 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??66 | ????EG | ????40 | ????A1 | ????100 | ????- | ????- | ??C2 | ????35 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??67 | ????EG | ????40 | ????A1 | ????100 | ????- | ????- | ??C2 | ????50 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??68 | ????EG | ????40 | ????A2 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??69 | ????EG | ????40 | ????A2 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??70 | ????EG | ????40 | ????A2 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??71 | ????EG | ????40 | ????A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??72 | ????EG | ????40 | ????A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??73 | ????EG | ????40 | ????A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??74 | ????EG | ????40 | ????B1 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??75 | ????EG | ????40 | ????B2 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??76 | ????EG | ????40 | ????B3 | ????100 | ????- | ????- | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??77 | ????EG | ????40 | ????B1 | ????90 | ????A1 | ????10 | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??78 | ????EG | ????40 | ????B1 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??79 | ????EG | ????- | ????A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??80 | ????EG | ????- | ????A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ??D3 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??81 | ????EG | ????- | ????A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ??D9 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??82 | ????ZN | ????40 | ????A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
| ??83 | ????GI | ????40 | ????A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ??D2 | ????5 | ??- | ????- | ??E17 | ????5 | ????1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silicon-dioxide that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 14
| Number | Performance | Note | |||||||||
| Dull and stereotyped solidity to corrosion | Solidity to corrosion behind the Sven-Gan Eriksson cut | Coating adhesion | Weldability | Resistance to compression system scratch property | Abrasion resistance | Anti-Texturized property | Kinetic friction coefficient | Thermolysis stability | |||
| Do not soak | Soak | ||||||||||
| ??1 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????800 | ????0.05 | ????○ | The present invention |
| ??2 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| ??3 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| ??4 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????400 | ????0.07 | ????○ | Comparative Examples |
| ??5 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????500 | ????0.05 | ????○ | The present invention |
| ??6 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????800 | ????0.05 | ????○ | The present invention |
| ??7 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????400 | ????0.05 | ????○ | Comparative Examples |
| ??8 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????500 | ????0.05 | ????○ | The present invention |
| ??9 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| ??10 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????900 | ????0.06 | ????○ | The present invention |
| ??11 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????450 | ????0.07 | ????○ | Comparative Examples |
| ??12 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????500 | ????0.05 | ????○ | The present invention |
| ??13 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????600 | ????0.05 | ????○ | The present invention |
| ??14 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????600 | ????0.06 | ????○ | The present invention |
| ??15 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????400 | ????0.08 | ????○ | The present invention |
| ??16 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????800 | ????0.05 | ????× | Comparative Examples |
| ??17 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1200 | ????0.06 | ????○ | The present invention |
| ??18 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1100 | ????0.05 | ????○ | The present invention |
| ??19 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????700 | ????0.06 | ????○ | The present invention |
| ??20 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????450 | ????0.10 | ????○ | Comparative Examples |
| ??21 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????800 | ????0.05 | ????× | Comparative Examples |
| ??22 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1200 | ????0.07 | ????○ | The present invention |
| ??23 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1100 | ????0.06 | ????○ | The present invention |
| ??24 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????700 | ????0.07 | ????○ | The present invention |
| ??25 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????450 | ????0.15 | ????○ | Comparative Examples |
| ??26 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????800 | ????0.05 | ????× | Comparative Examples |
| ??27 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1200 | ????0.07 | ????○ | The present invention |
| ??28 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1100 | ????0.06 | ????○ | The present invention |
| ??29 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????700 | ????0.07 | ????○ | The present invention |
| ??30 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????450 | ????0.10 | ????○ | Comparative Examples |
Table 15
| Number | Performance | Note | |||||||||
| Dull and stereotyped solidity to corrosion | Solidity to corrosion behind the Sven-Gan Eriksson cut | Coating adhesion | Weldability | Resistance to compression system scratch property | Abrasion resistance | Continuous slip pass | Kinetic friction coefficient | Thermolysis stability | |||
| Do not soak | Soak | ||||||||||
| 31 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????800 | ????0.05 | ????○ | The present invention |
| 32 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.06 | ????○ | The present invention |
| 33 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????900 | ????0.05 | ????○ | The present invention |
| 34 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1200 | ????0.06 | ????○ | The present invention |
| 35 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| 36 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1200 | ????0.06 | ????○ | The present invention |
| 37 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????800 | ????0.06 | ????○ | The present invention |
| 38 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????1100 | ????0.05 | ????○ | The present invention |
| 39 | ????○ | ????○ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????1500 | ????0.05 | ????○ | The present invention |
| 40 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????800 | ????0.06 | ????○ | The present invention |
| 41 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????1100 | ????0.05 | ????○ | The present invention |
| 42 | ????○ | ????○ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????1500 | ????0.05 | ????○ | The present invention |
| 43 | ????× | ????× | ????△ | ????△ | ????◎ | ????× | ????× | ????100 | ????0.08 | ????○ | Comparative Examples |
| 44 | ????○ | ????○ | ????○ | ????○ | ????◎ | ????○ | ????○ | ????500 | ????0.06 | ????○ | The present invention |
| 45 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| 46 | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????◎ | ????◎ | ????1500 | ????0.05 | ????○ | The present invention |
| 47 | ????◎ | ????◎ | ????◎ | ????○ | ????× | ????◎ | ????◎ | ????1800 | ????0.06 | ????○ | Comparative Examples |
| 48 | ????× | ????× | ????△ | ????△ | ????◎ | ????× | ????× | ????100 | ????0.08 | ????○ | Comparative Examples |
| 49 | ????○ | ????○ | ????○ | ????○ | ????◎ | ????○ | ????○ | ????500 | ????0.06 | ????○ | The present invention |
| 50 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| 51 | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????◎ | ????◎ | ????1500 | ????0.05 | ????○ | The present invention |
| 52 | ????◎ | ????◎ | ????◎ | ????○ | ????× | ????◎ | ????◎ | ????1800 | ????0.06 | ????○ | Comparative Examples |
| 53 | ????× | ????× | ????△ | ????△ | ????◎ | ????× | ????× | ????100 | ????0.08 | ????○ | Comparative Examples |
| 54 | ????○ | ????○ | ????○ | ????○ | ????◎ | ????○ | ????○ | ????500 | ????0.06 | ????○ | The present invention |
| 55 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| 56 | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????◎ | ????◎ | ????1500 | ????0.05 | ????○ | The present invention |
| 57 | ????◎ | ????◎ | ????◎ | ????○ | ????× | ????◎ | ????◎ | ????1800 | ????0.06 | ????○ | Comparative Examples |
| 58 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????△ | ????○ | ????800 | ????0.10 | ????○ | Comparative Examples |
| 59 | ????○ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????1000 | ????0.10 | ????○ | The present invention |
| 60 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.10 | ????○ | The present invention |
Table 16
| Number | Performance | Note | |||||||||
| Dull and stereotyped solidity to corrosion | Solidity to corrosion behind the Sven-Gan Eriksson cut | Coating adhesion | Weldability | Resistance to compression system scratch property | Abrasion resistance | Continuous slip pass | Kinetic friction coefficient | Thermolysis stability | |||
| Do not soak | Soak | ||||||||||
| 61 | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.10 | ????○ | The present invention |
| 62 | ????○ | ????○ | ????○ | ????△ | ????○ | ????△ | ????○ | ????1000 | ????0.10 | ????○ | Comparative Examples |
| 63 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????△ | ????○ | ????800 | ????0.10 | ????○ | Comparative Examples |
| 64 | ????○ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????1000 | ????0.10 | ????○ | The present invention |
| 65 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.10 | ????○ | The present invention |
| 66 | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.10 | ????○ | The present invention |
| 67 | ????○ | ????○ | ????○ | ????△ | ????○ | ????△ | ????○ | ????1000 | ????0.10 | ????○ | Comparative Examples |
| 68 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| 69 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????1000 | ????0.07 | ????○ | The present invention |
| 70 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| 71 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| 72 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????1000 | ????0.07 | ????○ | The present invention |
| 73 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| 74 | ????◎ | ????○ | ????○ | ????△ | ????◎ | ????◎ | ????◎ | ????2000 | ????0.06 | ????○ | The present invention |
| 75 | ????◎ | ????○ | ????○ | ????△ | ????◎ | ????◎ | ????◎ | ????2000 | ????0.06 | ????○ | The present invention |
| 76 | ????◎ | ????○ | ????○ | ????△ | ????◎ | ????◎ | ????◎ | ????2000 | ????0.06 | ????○ | The present invention |
| 77 | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????1800 | ????0.06 | ????○ | The present invention |
| 78 | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????1800 | ????0.06 | ????○ | The present invention |
| 79 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| 80 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????○ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| 81 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????1000 | ????0.05 | ????○ | The present invention |
| 82 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????1500 | ????0.05 | ????○ | The present invention |
| 83 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????2000 | ????0.05 | ????○ | The present invention |
Explained later is according to the embodiment of third aspect present invention.
(1) types of agents
The tabulation of agents useful for same is shown in Table 17.All lubricants (A) except that D7 all have 950-1000kg/m
3Density (as JIS K 6760 defineds), 0.2mm or lower hardness (acupuncture hardness) (as JIS K 2207 defineds), 80% or bigger degree of crystallinity (measuring) and 110-150 ℃ fusing point by X-ray diffraction.
The tabulation of table 17 reagent
| Reagent | Number | Name of product |
| Organic resin | A1 | Acrylic resin (AP-1508 (12), Toa Gosei Co., Ltd.) |
| A2 | Polyolefin-based water soluble resin (AR-2300, Toho Chemical Industry Co., Ltd.) | |
| A3 | The polyurethane-base water soluble resin (RA-85, Nippon-NSC) | |
| A4 | Epoxy group(ing) water soluble resin (DICFINE EM-60, Dainippon Ink and Chemicals Inc.) | |
| Silicate compound | B1 | Lithium silicate |
| B2 | Water glass | |
| B3 | Potassium silicate | |
| Colloided silica | C1 | Aqueous colloided silica (SNOWTEX N, Nissan Chemical Industries, Ltd.) |
| C2 | Aqueous colloided silica (SNOWTEX UP, Nissan Chemical Industries, Ltd.) | |
| Lubricant A﹠ contrast | D1 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 3.0 μ m) |
| D2 | Polyethylene (molecular weight: 8000, acid number: 0, granularity: 3.0 μ m) | |
| D3 | Polyethylene (molecular weight: 15000, acid number: 0, granularity: 3.0 μ m) | |
| D4 | Polyethylene (molecular weight: 20000, acid number: 0, granularity: 3.0 μ m) | |
| D5 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 0.1 μ m) | |
| D6 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 5.0 μ m) | |
| D7 | Modified poly ethylene (molecular weight: 1000, acid number: 20, granularity: 3.0 μ m) | |
| D8 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 3.0 μ m) | |
| D9 | Modified poly ethylene (molecular weight: 8000, acid number: 20, granularity: 3.0 μ m) | |
| D10 | Modified poly ethylene (molecular weight: 15000, acid number: 20, granularity: 3.0 μ m) | |
| D11 | Modified poly ethylene (molecular weight: 20000, acid number: 20, granularity: 3.0 μ m) | |
| D12 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 0.1 μ m) | |
| D13 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 5.0 μ m) | |
| D14 | Modified poly ethylene (molecular weight: 6000, acid number: 40, granularity: 3.0 μ m) | |
| D15 | Modified poly ethylene (molecular weight: 6000, acid number: 100, granularity: 3.0 μ m) | |
| Lubricant B﹠ contrast | E16 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 0.6 μ m) |
| E17 | Polyethylene (molecular weight: 5000, acid number: 0, granularity: 0.6 μ m) | |
| E18 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 3.0 μ m) | |
| E19 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 0.1 μ m) |
(2) type of metal sheet
Used metal sheet is listed those in the table 2.
(3) chromate treating
The carrying out of explaining at first aspect as the front.
(4) preparation of water-based organic/inorganic composite coating
Make from one of the water soluble resin of table 17 and silicate compound or two, colloided silica and lubricant prepare water-based organic/inorganic composite coating with table 18 to mixed shown in 20.
(5) coating of water-based organic/inorganic composite coating and drying
The water-based organic/inorganic composite coating of preparation in above (4) is applied on the overlay metallization plate of the chromate treating that obtains in above (3) and reaches listed dry weight among the table 18-20, baking and drying are made sample and are used for evaluation under 140 ℃ peak value metal temperature.Calculate the fraction of coverage of organic hybrid films according to the measurement of liquid film weight in the coating process.
(6) performance evaluation
A. the solidity to corrosion of plate
To estimate at the mode of being explained according to the embodiment of first aspect.
B. the solidity to corrosion behind the Sven-Gan Eriksson cut
To estimate at the mode of being explained according to the embodiment of first aspect.
C. coating adhesion
To estimate at the mode of being explained according to the embodiment of first aspect.
D. continuous welding
To estimate at the mode of being explained according to the embodiment of first aspect.
E. resistance to compression system abrades property
To estimate at the mode of being explained according to the embodiment of first aspect.
F. anti-upper layer lubricant separability test
Make each sample of preparation in above (5) stand above-mentioned rectangular drawing test 100 times continuously.After drawing continuously, visual assessment adheres to the situation of peeling off of the upper layer lubricant of mould.Zero opinion rating is judged to be satisfaction in the following evaluation criteria.
Zero: do not adhere to the lubricant substance accumulation
*: adhere to the lubricant substance accumulation
G. abrasion resistance test
To estimate at the mode of being explained according to the embodiment of first aspect.
H. static friction coefficient
To estimate at the mode of being explained according to the embodiment of first aspect.
I. kinetic friction coefficient
To estimate at the mode of being explained according to the embodiment of first aspect.
J. anti-Texturized property
To estimate at the mode of being explained according to the embodiment of first aspect.
Evaluation result is shown in table 21 in 23.These results clearly prove, technology of the present invention can be produced has the surface-treated metal plate that fabulous performance comprises solidity to corrosion, sticking power and weldability and fabulous resistance to compression system scratch property and processing property, also is suppressed in the pressing process generation that is broken away from the adhering residue that film causes by lubricant simultaneously.
Table 18
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silicon-dioxide that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 19
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silicon-dioxide that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 20
| Number | Metal sheet | Cr fraction of coverage (mg/m 2) | Organic/inorganic composite film (C) | Organic/inorganic composite membrane (0) | ||||||||||||||||
| Water soluble resin/silicate compound 1) | Lubricant (A) 3) | Lubricant (B) 3) | Fraction of coverage (g/m 2) | Water soluble resin/silicate compound 1) | Silicon-dioxide 2) | Fraction of coverage (g/m 2) | ||||||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | |||||
| ?59 | ??EG | ????40 | ?A1 | ??100 | ?- | ????- | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A1 | ????100 | ????- | ????- | ??C1 | ????35 | ????1.0 |
| ?60 | ??EG | ????40 | ?A1 | ??100 | ?- | ????- | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A1 | ????100 | ????- | ????- | ??C1 | ????50 | ????1.0 |
| ?61 | ??EG | ????40 | ?A1 | ??100 | ?- | ????- | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A1 | ????100 | ????- | ????- | ??C2 | ????0 | ????1.0 |
| ?62 | ??EG | ????40 | ?A1 | ??100 | ?- | ????- | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A1 | ????100 | ????- | ????- | ??C2 | ????5 | ????1.0 |
| ?63 | ??EG | ????40 | ?A1 | ??100 | ?- | ????- | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A1 | ????100 | ????- | ????- | ??C2 | ????10 | ????1.0 |
| ?64 | ??EG | ????40 | ?A1 | ??100 | ?- | ????- | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A1 | ????100 | ????- | ????- | ??C2 | ????35 | ????1.0 |
| ?65 | ??EG | ????40 | ?A1 | ??100 | ?- | ????- | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A1 | ????100 | ????- | ????- | ??C2 | ????50 | ????1.0 |
| ?66 | ??EG | ????40 | ?A2 | ??90 | ?A4 | ????10 | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A2 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ????1.0 |
| ?67 | ??EG | ????40 | ?A2 | ??90 | ?A4 | ????10 | ??D3 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A2 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ????1.0 |
| ?68 | ??EG | ????40 | ?A2 | ??90 | ?A4 | ????10 | ??D9 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A2 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ????1.0 |
| ?69 | ??EG | ????40 | ?A3 | ??90 | ?A4 | ????10 | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ????1.0 |
| ?70 | ??EG | ????40 | ?A3 | ??90 | ?A4 | ????10 | ??D3 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ????1.0 |
| ?71 | ??EG | ????40 | ?A3 | ??90 | ?A4 | ????10 | ??D9 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ????1.0 |
| ?72 | ??EG | ????40 | ?B1 | ??100 | ?- | ????- | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??B1 | ????100 | ????- | ????- | ??C1 | ????15 | ????1.0 |
| ?73 | ??EG | ????40 | ?B2 | ??100 | ?- | ????- | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??B2 | ????100 | ????- | ????- | ??C1 | ????15 | ????1.0 |
| ?74 | ??EG | ????40 | ?B3 | ??100 | ?- | ????- | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??B3 | ????100 | ????- | ????- | ??C1 | ????15 | ????1.0 |
| ?75 | ??EG | ????40 | ?B1 | ??90 | ?A1 | ????10 | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??B1 | ????90 | ????A1 | ????10 | ??C1 | ????15 | ????1.0 |
| ?76 | ??EG | ????40 | ?B1 | ??90 | ?A4 | ????10 | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??B1 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ????1.0 |
| ?77 | ??EG | ????- | ?A3 | ??90 | ?A4 | ????10 | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ????1.0 |
| ?78 | ??EG | ????- | ?A3 | ??90 | ?A4 | ????10 | ??D3 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ????1.0 |
| ?79 | ??EG | ????- | ?A3 | ??90 | ?A4 | ????10 | ??D9 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ????1.0 |
| ?80 | ??ZN | ????40 | ?A3 | ??90 | ?A4 | ????10 | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ????1.0 |
| ?81 | ??GI | ????40 | ?A3 | ??90 | ?A4 | ????10 | ??D2 | ????40 | ??- | ??- | ??- | ??- | ????0.2 | ??A3 | ????90 | ????A4 | ????10 | ??C1 | ????15 | ????1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silicon-dioxide that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 21
| Number | Performance | Note | ||||||||||
| Dull and stereotyped solidity to corrosion | Solidity to corrosion behind the Sven-Gan Eriksson cut | Coating adhesion | Weldability | Resistance to compression system scratch property | Abrasion resistance | Stripper-resistance | Anti-Texturized property | Kinetic friction coefficient | Static friction coefficient | |||
| Do not soak | Soak | |||||||||||
| ??1 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.07 | ????0.15 | The present invention |
| ??2 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| ??3 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????○ | ????0.15 | ????0.25 | The present invention |
| ??4 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????△ | ????○ | ????○ | ????○ | ????0.20 | ????0.30 | Comparative Examples |
| ??5 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????○ | ????0.08 | ????0.15 | The present invention |
| ??6 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.07 | ????0.12 | The present invention |
| ??7 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????× | ????0.06 | ????0.10 | Comparative Examples |
| ??8 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.09 | ????0.20 | The present invention |
| ??9 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.25 | The present invention |
| ??10 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| ??11 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????× | ????△ | ????○ | ????○ | ????0.20 | ????0.35 | Comparative Examples |
| ??12 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????○ | ????0.08 | ????0.20 | The present invention |
| ??13 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.07 | ????0.17 | The present invention |
| ??14 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| ??15 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????× | ????× | ????○ | ????○ | ????0.20 | ????0.35 | Comparative Examples |
| ??16 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| ??17 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| ??18 | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| ??19 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| ??20 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| ??21 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.25 | The present invention |
| ??22 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.25 | The present invention |
| ??23 | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.25 | The present invention |
| ??24 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.25 | The present invention |
| ??25 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.25 | The present invention |
| ??26 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????○ | ????0.12 | ????0.25 | The present invention |
| ??27 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| ??28 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????○ | ????0.20 | ????0.35 | The present invention |
| ??29 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| ??30 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
Table 22
| Number | Performance | Note | ||||||||||
| Dull and stereotyped solidity to corrosion | Solidity to corrosion behind the Sven-Gan Eriksson cut | Coating adhesion | Weldability | Resistance to compression system scratch property | Abrasion resistance | Stripper-resistance | Anti-Texturized property | Kinetic friction coefficient | Static friction coefficient | |||
| Do not soak | Soak | |||||||||||
| ??31 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| ??32 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| ??33 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????○ | ????0.12 | ????0.25 | The present invention |
| ??34 | ????○ | ????○ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| ??35 | ????△ | ????△ | ????○ | ????△ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| ??36 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????○ | ????0.20 | ????0.35 | The present invention |
| ??37 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????○ | ????0.18 | ????0.30 | The present invention |
| ??38 | ????○ | ????○ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| ??39 | ????△ | ????△ | ????○ | ????△ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| ??40 | ????× | ????× | ????△ | ????△ | ????◎ | ????× | ????× | ????× | ????○ | ????0.08 | ????0.15 | Comparative Examples |
| ??41 | ????○ | ????○ | ????○ | ????○ | ????◎ | ????○ | ????○ | ????○ | ????○ | ????0.08 | ????0.15 | The present invention |
| ??42 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| ??43 | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.30 | The present invention |
| ??44 | ????◎ | ????◎ | ????◎ | ????○ | ????× | ????◎ | ????◎ | ????○ | ????○ | ????0.25 | ????0.35 | Comparative Examples |
| ??45 | ????× | ????× | ????△ | ????△ | ????◎ | ????× | ????× | ????× | ????○ | ????0.08 | ????0.15 | Comparative Examples |
| ??46 | ????○ | ????○ | ????○ | ????○ | ????◎ | ????○ | ????○ | ????○ | ????○ | ????0.08 | ????0.20 | The present invention |
| ??47 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.25 | The present invention |
| ??48 | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.25 | The present invention |
| ??49 | ????◎ | ????◎ | ????◎ | ????○ | ????× | ????◎ | ????◎ | ????○ | ????○ | ????0.25 | ????0.35 | Comparative Examples |
| ??50 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????× | ????× | ????○ | ????○ | ????0.2 | ????0.30 | Comparative Examples |
| ??51 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????○ | ????0.15 | ????0.25 | The present invention |
| ??52 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.1 | ????0.20 | The present invention |
| ??53 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????× | ????× | ????○ | ????○ | ????0.20 | ????0.30 | Comparative Examples |
| ??54 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| ??55 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.25 | The present invention |
| ??56 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????△ | ????○ | ????○ | ????○ | ????0.10 | ????0.20 | Comparative Examples |
| ??57 | ????○ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| ??58 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
Table 23
| Number | Performance | Note | ||||||||||
| Dull and stereotyped solidity to corrosion | Solidity to corrosion behind the Sven-Gan Eriksson cut | Coating adhesion | Weldability | Resistance to compression system scratch property | Abrasion resistance | Stripper-resistance | Anti-Texturized property | Kinetic friction coefficient | Static friction coefficient | |||
| Do not soak | Soak | |||||||||||
| 59 | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| 60 | ????○ | ????○ | ????○ | ????△ | ????○ | ????△ | ????○ | ????○ | ????○ | ????0.10 | ????0.20 | Comparative Examples |
| 61 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????△ | ????○ | ????○ | ????○ | ????0.10 | ????0.20 | Comparative Examples |
| 62 | ????○ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| 63 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| 64 | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????1.00 | ????0.20 | The present invention |
| 65 | ????○ | ????○ | ????○ | ????△ | ????○ | ????△ | ????○ | ????○ | ????○ | ????0.10 | ????0.20 | Comparative Examples |
| 66 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| 67 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????○ | ????0.15 | ????0.25 | The present invention |
| 68 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| 69 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| 70 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????○ | ????0.15 | ????0.25 | The present invention |
| 71 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| 72 | ????◎ | ????○ | ????○ | ????△ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.25 | The present invention |
| 73 | ????◎ | ????○ | ????○ | ????△ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.15 | ????0.30 | The present invention |
| 74 | ????◎ | ????○ | ????○ | ????△ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.25 | The present invention |
| 75 | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.25 | The present invention |
| 76 | ????◎ | ????◎ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.25 | The present invention |
| 77 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| 78 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????○ | ????◎ | ????○ | ????○ | ????0.15 | ????0.25 | The present invention |
| 79 | ????△ | ????△ | ????◎ | ????○ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| 80 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
| 81 | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????0.10 | ????0.20 | The present invention |
Industrial applicibility
Surface-treated metal plate according to first aspect present invention shows the performance of excellent corrosion resistance, adhesive force and solderability and keeps resistance to compression system scratch property, also improve simultaneously in the section bundling process because reeling loose or the folding problem that causes the coiled material fragmentation of load, thereby be suitable as the material in household electrical appliance, construction material and the automotive field. Water-based organic/inorganic composite coating and manufacture method according to first aspect present invention provide satisfied resistance to compression system scratch property and anti-Texturized property for commercially available surface-treated metal plate.
Surface-treated metal plate according to second aspect present invention shows the performance of excellent corrosion resistance, adhesive force and solderability and keeps resistance to compression system scratch property and anti-continuous skimming wear, thereby is suitable as the material in household electrical appliance, construction material and the automotive field. Water-based organic/inorganic composite coating and manufacture method according to second aspect present invention provide satisfied resistance to compression system scratch property and anti-continuous skimming wear for commercially available surface-treated metal plate.
Surface-treated metal plate according to third aspect present invention shows the performance of excellent corrosion resistance, adhesive force and solderability and keeps resistance to compression system scratch property, also improve simultaneously in the section bundling process and to cause the problem of coiled material fragmentation because the loose or load of reeling is folding and to be suppressed in the pressing process generation that is broken away from the adhering residue thing that film causes by lubricant, thereby be suitable as the material in household electrical appliance, construction material and the automotive field. Water-based organic/inorganic composite coating and manufacture method according to third aspect present invention provide satisfied resistance to compression system scratch property and anti-Texturized property for commercially available surface-treated metal plate.
Claims (22)
1. the surface-treated metal plate of a resistance to compression system scratch property and anti-Texturized property excellence is characterised in that to have 0.3-5.0g/m
2Comprise polyolefin-wax dispersion that one of water soluble resin and silicate compound or both and molecular weight are 6000-15000 and by the water-based organic/inorganic composite membrane of the colloidal silica of solid content 5-35% weight.
2. the surface-treated metal plate of the resistance to compression system of claim 1 scratch property and anti-Texturized property excellence, be characterised in that described polyolefin-wax dispersion be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a in the modified polyolefin wax dispenser of 0.1-5.0 μ m.
3. the surface-treated metal plate of claim 1 or 2 resistance to compression system scratch property and anti-Texturized property excellence, the kinetic friction coefficient that is characterised in that described surface is 0.07-0.15, static friction coefficient is 0.10 or higher.
4. a water-based organic/inorganic composite coating is characterised in that to comprise polyolefin-wax dispersion, the colloidal silica by solid content 5-35% weight, the He Shui that one of water soluble resin and silicate compound or both and molecular weight are 6000-15000.
5. the water-based organic/inorganic composite coating of claim 4, be characterised in that described polyolefin-wax dispersion be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a in the modified polyolefin wax dispenser of 0.1-5.0 μ m.
6. the manufacture method of the surface-treated metal plate of resistance to compression system scratch property and anti-Texturized property excellence, be characterised in that coating with claim 4 by dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
7. the manufacture method of the surface-treated metal plate of resistance to compression system scratch property and anti-Texturized property excellence, be characterised in that coating with claim 5 by dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
8. a resistance to compression system abrades property and the surface-treated metal plate that resists continuous skimming wear excellence, be characterised in that to have and comprise one of water soluble resin and silicate compound or both and be the lubricant (A) formed of the polyolefin-wax dispersion of 6000-15000, be the lubricant (B) formed of the polyolefin-wax dispersion of 1000-5000 and by the water-based organic/inorganic composite membrane of the colloidal silica of solid content 5-35% weight with have 0.3-5.0g/m by molecular weight by molecular weight
2Described water-based organic/inorganic composite membrane.
9. the resistance to compression system of claim 8 abrades the surface-treated metal plate of property and anti-continuous skimming wear excellence, be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the modified polyolefin wax dispenser of 0.1-5.0 μ m, lubricant (B) is that polar functionalities, molecular weight are not that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-5.0 μ m.
10. water-based organic/inorganic composite coating comprises one of water soluble resin and silicate compound or both and is the lubricant (A) formed of the polyolefin-wax dispersion of 6000-15000, is lubricant (B), the colloidal silica by solid content 5-35% weight, the He Shui that the polyolefin-wax dispersion of 1000-5000 is formed by molecular weight by molecular weight.
11. the water-based organic/inorganic composite coating of claim 10, be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the modified polyolefin wax dispenser of 0.1-5.0 μ m, lubricant (B) is that polar functionalities, molecular weight are not that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-5.0 μ m.
12. the manufacture method of the surface-treated metal plate of resistance to compression system scratch property and the moving abradability excellence of antiskid, be characterised in that water-based organic/inorganic composite coating with claim 10 by dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
13. the manufacture method of the surface-treated metal plate of resistance to compression system scratch property and anti-continuous skimming wear excellence, be characterised in that water-based organic/inorganic composite coating with claim 11 by dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
14. the surface-treated metal plate of a resistance to compression system scratch property and anti-Texturized property excellence is characterised in that to have 0.05-0.3g/m
2Dry weight comprise one of water soluble resin and silicate compound or both and by molecular weight be the water-based organic/inorganic composite membrane (C) of the lubricant (A) formed of the polyolefin-wax dispersion of 6000-15000 as the first layer, and 0.5-5.0g/m
2The water-based organic/inorganic composite membrane of forming by one of water soluble resin and silicate compound or both with by the colloidal silica of solid content 5-35% weight (D) of dry weight is as the second layer.
15. the surface-treated metal plate of the resistance to compression system of claim 14 scratch property and anti-Texturized property excellence, be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the modified polyolefin wax dispenser of 0.1-5.0 μ m.
16. the surface-treated metal plate of the resistance to compression system of claim 14 or 15 scratch property and anti-Texturized property excellence is characterised in that described water-based organic/inorganic composite membrane (C) is that the compounded lubricant that the lubricant (B) of the lubricant (A) of polyolefin-wax dispersion of 6000-15000 and the polyolefin-wax dispersion that molecular weight is 1000-5000 is mixed with is formed by water soluble resin and by molecular weight.
17. the surface-treated metal plate of the resistance to compression system of claim 16 scratch property and anti-Texturized property excellence, be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the modified polyolefin wax dispenser of 0.1-5.0 μ m, lubricant (B) is that polar functionalities, molecular weight are not that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-3.0 μ m.
18. the surface-treated metal plate of the resistance to compression system of each of claim 14 to 17 scratch property and anti-Texturized property excellence, the kinetic friction coefficient that is characterised in that described surface is 0.07-0.15, and static friction coefficient is 0.10 or higher.
19. the manufacture method of the surface-treated metal plate of resistance to compression system scratch property and anti-Texturized property excellence is characterised in that on overlay metallization plate coating is that the lubricant (A) of polyolefin-wax dispersion of 6000-15000 and the water-based organic/inorganic composite coating (E) that water is formed extremely reach 0.05-0.3g/m by dry weight basis by one of water soluble resin and silicate compound or both and molecular weight
2Afterwards, baking forms the first layer, be coated with then by one of water soluble resin and silicate compound or both and wherein colloidal silica content count the colloidal silica of 5-35% weight by solid content and water-based organic/inorganic composite coating (F) that water is formed extremely reaches 0.5-5.0g/m by dry weight basis
2, baking forms the second layer.
20. the manufacture method of the surface-treated metal plate of the resistance to compression system of claim 19 scratch property and anti-Texturized property excellence, be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the modified polyolefin wax dispenser of 0.1-5.0 μ m.
21. the manufacture method of the surface-treated metal plate of the resistance to compression system of claim 19 or 20 scratch property and anti-Texturized property excellence is characterised in that described water-based organic/inorganic composite coating (E) is that compounded lubricant and the water that the lubricant (B) of the lubricant (A) of polyolefin-wax dispersion of 6000-15000 and the polyolefin-wax dispersion that molecular weight is 1000-5000 is mixed with is formed by water soluble resin, by molecular weight.
22. the manufacture method of the surface-treated metal plate of the resistance to compression system of each of claim 19 to 21 scratch property and anti-Texturized property excellence, be characterised in that described lubricant (A) is to be selected from not polar functionalities, molecular weight is that 6000-15000 and granularity are the polyolefin-wax dispersion of 0.1-5.0 μ m, with molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the modified polyolefin wax dispenser of 0.1-5.0 μ m, lubricant (B) is a polar functionalities not, molecular weight is that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-3.0 μ m.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12319/2001 | 2001-01-19 | ||
| JP2001012321A JP2002212747A (en) | 2001-01-19 | 2001-01-19 | Surface treated metallic sheet having excellent press galling resistance and continuous sliding friction resistance, and method for manufacturing the same |
| JP12321/2001 | 2001-01-19 | ||
| JP2001012319A JP2002212754A (en) | 2001-01-19 | 2001-01-19 | Surface treated metallic sheet having excellent press galling resistance and coil deformation resistance, and method for manufacturing the same |
| JP2001012347A JP4132686B2 (en) | 2001-01-19 | 2001-01-19 | Surface-treated metal plate excellent in press galling resistance and coil deformation resistance and method for producing the same |
| JP12347/2001 | 2001-01-19 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100906977A Division CN100368098C (en) | 2001-01-19 | 2002-01-18 | Surface-treated metal sheets excellent in press dragging resistance and coil deformation resistance and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1488010A true CN1488010A (en) | 2004-04-07 |
| CN1276995C CN1276995C (en) | 2006-09-27 |
Family
ID=27345770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02803860 Expired - Lifetime CN1276995C (en) | 2001-01-19 | 2002-01-18 | Surface-treated metal sheets excellent in press dragging resistance and coil deformation resistance and process for producing the same |
Country Status (5)
| Country | Link |
|---|---|
| KR (2) | KR100543157B1 (en) |
| CN (1) | CN1276995C (en) |
| MY (1) | MY128667A (en) |
| TW (1) | TW573062B (en) |
| WO (1) | WO2002057510A1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3512564A1 (en) * | 1985-04-06 | 1986-10-16 | Basf Ag, 6700 Ludwigshafen | AQUEOUS WAX DISPERSIONS AS PRESERVATIVES FOR METAL AND VARNISH SURFACES, THEIR USE AND A METHOD FOR TEMPORARY PRESERVATION OF METAL AND VARNISH SURFACES |
| JP3174503B2 (en) * | 1996-04-01 | 2001-06-11 | 新日本製鐵株式会社 | Method for producing surface-treated steel sheet with excellent press workability |
| JP2000239690A (en) * | 1998-12-25 | 2000-09-05 | Nippon Parkerizing Co Ltd | Water-based metal surface treating composition for forming lubricating film excellent in scratch resistance |
-
2002
- 2002-01-18 MY MYPI20020196 patent/MY128667A/en unknown
- 2002-01-18 TW TW91100807A patent/TW573062B/en not_active IP Right Cessation
- 2002-01-18 CN CN 02803860 patent/CN1276995C/en not_active Expired - Lifetime
- 2002-01-18 WO PCT/JP2002/000359 patent/WO2002057510A1/en not_active Application Discontinuation
- 2002-01-18 KR KR1020037009542A patent/KR100543157B1/en active IP Right Grant
- 2002-01-18 KR KR1020057019813A patent/KR20050105288A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| MY128667A (en) | 2007-02-28 |
| CN1276995C (en) | 2006-09-27 |
| WO2002057510A1 (en) | 2002-07-25 |
| KR20030077580A (en) | 2003-10-01 |
| KR100543157B1 (en) | 2006-01-20 |
| TW573062B (en) | 2004-01-21 |
| KR20050105288A (en) | 2005-11-03 |
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Granted publication date: 20060927 |